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The Handbook of Environmental Chemistry

Founded by Otto Hutzinger

Editors-in-Chief: Damià Barceló l Andrey G. Kostianoy

Volume 23

Advisory Board:
Jacob de Boer, Philippe Garrigues, Ji-Dong Gu,
Kevin C. Jones, Thomas P. Knepper, Alice Newton,
Donald L. Sparks
The Handbook of Environmental Chemistry
Recently Published and Forthcoming Volumes

Global Risk-Based Management of Effect-Directed Analysis of Complex
Chemical Additives II: Risk-Based Environmental Contamination
Assessment and Management Strategies Volume Editor: W. Brack
Volume Editors: B. Bilitewski, R.M. Darbra, Vol. 15, 2011
and D. Barceló
Vol. 23, 2013 Waste Water Treatment and Reuse
in the Mediterranean Region
Chemical Structure of Pelagic Redox Volume Editors: D. Barceló and M. Petrovic
Interfaces: Observation and Modeling Vol. 14, 2011
Volume Editor: E.V. Yakushev
Vol. 22, 2013 The Ebro River Basin
Volume Editors: D. Barceló and M. Petrovic
The Llobregat: The Story of a Polluted Vol. 13, 2011
Mediterranean River
Volume Editors: S. Sabater, A. Ginebreda, Polymers – Opportunities and Risks II:
and D. Barceló Sustainability, Product Design
Vol. 21, 2012 and Processing
Volume Editors: P. Eyerer, M. Weller,
Emerging Organic Contaminants and C. Hübner
and Human Health Vol. 12, 2010
Volume Editor: D. Barceló
Vol. 20, 2012 Polymers – Opportunities and Risks I:
General and Environmental Aspects
Volume Editor: P. Eyerer
Emerging and Priority Pollutants in Vol. 11, 2010
Rivers: Bringing Science into River
Management Plans Chlorinated Paraffins
Volume Editors: H. Guasch, A. Ginebreda, Volume Editor: J. de Boer
and A. Geiszinger Vol. 10, 2010
Vol. 19, 2012
Biodegradation of Azo Dyes
Global Risk-Based Management of Volume Editor: H. Atacag Erkurt
Chemical Additives I: Production, Vol. 9, 2010
Usage and Environmental Occurrence
Volume Editors: B. Bilitewski, R.M. Darbra, Water Scarcity in the Mediterranean:
and D. Barceló Perspectives Under Global Change
Vol. 18, 2012 Volume Editors: S. Sabater
and D. Barceló
Polyfluorinated Chemicals and Vol. 8, 2010
Transformation Products
Volume Editors: T.P. Knepper The Aral Sea Environment
and F.T. Lange Volume Editors: A.G. Kostianoy
Vol. 17, 2012 and A.N. Kosarev
Vol. 7, 2010
Brominated Flame Retardants Alpine Waters
Volume Editors: E. Eljarrat and D. Barceló Volume Editor: U. Bundi
Vol. 16, 2011 Vol. 6, 2010
Global Risk-Based
Management of
Chemical Additives II
Risk-Based Assessment and Management
Strategies

Volume Editors: Bernd Bilitewski  Rosa Mari Darbra 
Damià Barceló

With contributions by

S. Åström  D. Baderna  N.G. Bakhtyari  D. Barceló  E. Benfenati 
B. Bilitewski  E. Boriani  E. Capri  J. Casal  A. Colacci 
R.M. Darbra  J.L. Domingo  Z. Fonseca  H. Friege  A. Ginebreda 
N. Golbamaki  M. Gros  V. Grundmann  D. Guillén  S. Heise 
R. Hooda  A. Kersten  U. Lahl  H.F. Larsen  M. Lindblad 
S. Maggioni  C.F. Mahler  A. Mishra  M. Nadal  N.B. Ngoc 
H.-G. Ni  S. Pandey  M. Petrovic  H.-J. Putz  J. Rovira  T. Rydberg 
S. Rydin  S. Schabel  A.S. Schueler  M. Schuhmacher  X. Seguí 
X. Segui  S. Sthiannopkao  N.A. Suciu  N. Suciu  T. Tanaka 
T. Tanaku  H. Tien  N.T.D. Trang  M. Trevisan  M. Vaccari 
E. van der Voet  L. van Oers  J. Westerdahl  A. Zehm  E.Y. Zeng 
B. Zeschmar-Lahl
Editors
Prof. Dr. Ing. habil. Dr. h.c. Bernd Bilitewski Prof. Dr. Damià Barceló
Dresden University of Technology Department of Environmental Chemistry
Institute of Waste Management and IDAEA-CSIC
Contaminated Site Treatment Barcelona, Spain
Pirna, Germany and
Catalan Institute for Water Research (ICRA)
Assoc. Prof. Dr. Rosa Mari Darbra Scientific and Technological Park of the
CERTEC – Centre for Technological University of Girona
Risk Studies Girona, Spain
UPC – Polytechnic University of
Catalonia
Barcelona, Spain

The Handbook of Environmental Chemistry
ISSN 1867-979X ISSN 1616-864X (electronic)
ISBN 978-3-642-34571-5 ISBN 978-3-642-34572-2 (eBook)
DOI 10.1007/978-3-642-34572-2
Springer Heidelberg New York Dordrecht London
Library of Congress Control Number: 2012956537

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Printed on acid-free paper

Springer is part of Springer Science+Business Media (www.springer.com)
In Memoriam Otto Hutzinger 1933–2012
Editors-in-Chief
Prof. Dr. Damià Barceló Prof. Dr. Andrey G. Kostianoy
Department of Environmental Chemistry P.P. Shirshov Institute of Oceanology
IDAEA-CSIC Russian Academy of Sciences
C/Jordi Girona 18–26 36, Nakhimovsky Pr.
08034 Barcelona, Spain 117997 Moscow, Russia
and kostianoy@gmail.com
Catalan Institute for Water Research (ICRA)
H20 Building
Scientific and Technological Park of the
University of Girona
Emili Grahit, 101
17003 Girona, Spain
dbcqam@cid.csic.es

Advisory Board
Prof. Dr. Jacob de Boer
IVM, Vrije Universiteit Amsterdam, The Netherlands

Prof. Dr. Philippe Garrigues
University of Bordeaux, France

Prof. Dr. Ji-Dong Gu
The University of Hong Kong, China

Prof. Dr. Kevin C. Jones
University of Lancaster, United Kingdom

Prof. Dr. Thomas Knepper
University of Applied Science, Fresenius, Idstein, Germany

Prof. Dr. Alice Newton
University of Algarve, Faro, Portugal

Prof. Dr. Donald L. Sparks
Plant and Soil Sciences, University of Delaware, USA

vii
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Aims and Scope

Since 1980, The Handbook of Environmental Chemistry has provided sound
and solid knowledge about environmental topics from a chemical perspective.
Presenting a wide spectrum of viewpoints and approaches, the series now covers
topics such as local and global changes of natural environment and climate;
anthropogenic impact on the environment; water, air and soil pollution; remediation
and waste characterization; environmental contaminants; biogeochemistry; geo-
ecology; chemical reactions and processes; chemical and biological transformations
as well as physical transport of chemicals in the environment; or environmental
modeling. A particular focus of the series lies on methodological advances in
environmental analytical chemistry.

ix
Series Preface

With remarkable vision, Prof. Otto Hutzinger initiated The Handbook of Environ-
mental Chemistry in 1980 and became the founding Editor-in-Chief. At that time,
environmental chemistry was an emerging field, aiming at a complete description
of the Earth’s environment, encompassing the physical, chemical, biological, and
geological transformations of chemical substances occurring on a local as well as a
global scale. Environmental chemistry was intended to provide an account of the
impact of man’s activities on the natural environment by describing observed
changes.
While a considerable amount of knowledge has been accumulated over the last
three decades, as reflected in the more than 70 volumes of The Handbook of
Environmental Chemistry, there are still many scientific and policy challenges
ahead due to the complexity and interdisciplinary nature of the field. The series
will therefore continue to provide compilations of current knowledge. Contribu-
tions are written by leading experts with practical experience in their fields. The
Handbook of Environmental Chemistry grows with the increases in our scientific
understanding, and provides a valuable source not only for scientists but also for
environmental managers and decision-makers. Today, the series covers a broad
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ical advances in environmental analytical chemistry.
In recent years, there has been a growing tendency to include subject matter of
societal relevance in the broad view of environmental chemistry. Topics include
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topics are of great importance for the development and acceptance of The Hand-
book of Environmental Chemistry, the publisher and Editors-in-Chief have decided
to keep the handbook essentially a source of information on “hard sciences” with a
particular emphasis on chemistry, but also covering biology, geology, hydrology
and engineering as applied to environmental sciences.
The volumes of the series are written at an advanced level, addressing the needs
of both researchers and graduate students, as well as of people outside the field of
“pure” chemistry, including those in industry, business, government, research
establishments, and public interest groups. It would be very satisfying to see
these volumes used as a basis for graduate courses in environmental chemistry.
With its high standards of scientific quality and clarity, The Handbook of

xi
xii Series Preface

Environmental Chemistry provides a solid basis from which scientists can share
their knowledge on the different aspects of environmental problems, presenting a
wide spectrum of viewpoints and approaches.
The Handbook of Environmental Chemistry is available both in print and online
via www.springerlink.com/content/110354/. Articles are published online as soon
as they have been approved for publication. Authors, Volume Editors and Editors-
in-Chief are rewarded by the broad acceptance of The Handbook of Environmental
Chemistry by the scientific community, from whom suggestions for new topics to
the Editors-in-Chief are always very welcome.

Damià Barceló
Andrey G. Kostianoy
Editors-in-Chief
Volume Preface

This second volume of this book, Global Risk-Based Management of Chemical
Additives, presents the results obtained after 3 years of research conducted during
the EC funded RISKCYCLE project (Risk-based management of chemicals and
products in a circular economy at a global scale).
The main objective of this project was to establish and coordinate a global
network of European and international experts and stakeholders from worldwide
countries to assess the risks of hazardous chemicals and additives contained in
different daily products. The transport of these compounds is given at a global
scale, increasing their potential damage to the environment and citizens all over the
world.
In the first part of this book, different models related to the assessment of the
potential risk posed by the chemical additives are presented. These models come
from different fields of expertise: toxicology, risk assessment, chemicals fate and
exposure, life cycle assessment, economics, etc. The potential benefits of the
different models as well as their drawbacks are analyzed in order to select some
of them for the application to particular case studies.
Some aspects related to the chemicals regulations are also reviewed, especially
those affecting the European new chemicals legislation, such as REACH (regula-
tion concerning the Registration, Evaluation, Authorizations and restriction of
Chemicals). Some socioeconomic aspects are also treated in relation to the need
of chemicals for the society.
In the second part, specific case studies in which the aforementioned models
have been applied are presented. The results of such application as well as their
reliability are discussed. Toxicological studies in Italy, risk assessment of electronic
waste in China, or disposal of bearing lamps in India are some examples of selected
scenarios.We hope that the scientific community finds in this book a source of
information and inspiration to continue the research on chemical additives
contained in products around the world.
Finally, we would like to thank all the authors who have contributed to this book,
for their effort in gathering the information and elaborating the different chapters.
We are also grateful that the advisory board of the project was helping us to keep

xiii
xiv Volume Preface

realism in the project discussions. We would like to mention especially Dr. Jürgen
Büsing, scientific officer from the Commission DG Research, for his help and his
guiding comments.

Georges Deschamps
EC Project Officer
B. Bilitewski, R.M. Darbra, D. Barceló
Editors
Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
D. Barceló, R.M. Darbra, B. Bilitewski, V. Grundmann, and A. Zehm

Part I Methodologies for the Global Management Strategies

Life Cycle Assessment of Additives: Methodology and Data . . . . . . . . . . . . . . . 7
Ester van der Voet, Lauran van Oers, Tomas Rydberg, Jenny Westerdahl,
and Henrik Fred Larsen

Characterization of Environmental Exposure: Measuring
Versus Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Daniel Guillén, Antoni Ginebreda, Rosa M. Darbra, Meritxell Gros,
Mira Petrovic, and Damià Barceló

Environmental Fate Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
N. Suciu, T. Tanaka, M. Trevisan, M. Schuhmacher, M. Nadal, J. Rovira,
X. Segui, J. Casal, R.M. Darbra, and E. Capri

Toxicological and Ecotoxicological Studies for Additives . . . . . . . . . . . . . . . . . . 73
Nazanin Golbamaki Bakhtyari, Diego Baderna, Elena Boriani,
Marta Schuhmacher, Susanne Heise, and Emilio Benfenati

A Revision of Current Models for Environmental and Human Health
Impact and Risk Assessment for Application to Emerging Chemicals . . . 91
J. Rovira, M. Nadal, J.L. Domingo, T. Tanaku, N.A. Suciu, M. Trevisan,
E. Capri, X. Seguı́, R.M. Darbra, and M. Schuhmacher

Are Chemicals in Products Good or Bad for the Society? –
An Economic Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
Stefan Åström, Maria Lindblad, Jenny Westerdahl, and Tomas Rydberg

RISKCYCLE and EU Legislation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
Uwe Lahl and Barbara Zeschmar-Lahl

xv
xvi Contents

Part II Case Studies

Two Sides of One Coin: Relations Between Hazardous Substances
and Valuable Resources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
Henning Friege

Toxicological Characterization of Waste-Related Products
Using Alternative Methods: Three Case Studies . . . . . . . . . . . . . . . . . . . . . . . . . . 171
Diego Baderna, Nazanin Golbamaki, Silvia Maggioni, Monica Vaccari,
Annamaria Colacci, and Emilio Benfenati

LCA Case Study on Printed Matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
Henrik Fred Larsen

LCA Case Study Cushion Vinyl Floor Covering and DEHP . . . . . . . . . . . . . 223
Lauran van Oers and Ester van der Voet

Chemicals in Leather: International Trends on Risk-Based Control
and Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
Stefan Rydin

Managing E-Waste in Developed and Developing Countries . . . . . . . . . . . . . 263
Suthipong Sthiannopkao

Mass Emissions of Pollutants from E-Waste Processed in China
and Human Exposure Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
Hong-Gang Ni and Eddy Y. Zeng

Tracking Global Flows of E-Waste Additives by Using Substance
Flow Analysis, with a Case Study in China . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
H. Tien, S. Heise, X. Seguı́, J. Casal, R.M. Darbra, N. Suciu, E. Capri,
M. Trevisan, M. Schuhmacher, M. Nadal, and J. Rovira

Human and Environmental Impact Produced by E-Waste Releases
at Guiyu Region (China) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
N. Suciu, E. Capri, M. Trevisan, T. Tanaka, H. Tien, S. Heise,
M. Schuhmacher, M. Nadal, J. Rovira, X. Seguı́, J. Casal, and R.M. Darbra

In Search of Zero Waste: An Experiment in Progress . . . . . . . . . . . . . . . . . . . . 385
C.F. Mahler, A.S. Schueler, and Z. Fonseca

Mineral Oil in Board and Paper Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
Antje Kersten, Hans-Joachim Putz, and Samuel Schabel
Contents xvii

Proposed Plan for Disposal of Mercury- Bearing Lamps for India . . . . . . 419
Suneel Pandey, Rakesh Hooda, and Arabinda Mishra

Study of the Substitution of Fossil Fuels by RDF Produced
from Municipal Solid Waste of Hanoi: A Case Study . . . . . . . . . . . . . . . . . . . . . 441
Nguyen Thi Diem Trang and N.B. Ngoc

Part III Conclusions

Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 465
B. Bilitewski, A. Zehm, V. Grundmann, R.M. Darbra, and D. Barceló

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
Introduction

D. Barceló, R.M. Darbra, B. Bilitewski, V. Grundmann, and A. Zehm

Abstract Chemicals are part of different daily products due to the characteristics
that they provide to them. However, their release into the environment during the
end of the product’s life can affect harmfully the environment and the citizens. The
worldwide transport of these chemicals at a global scale increases this negative
potential effect. In this sense, initiatives such as the RISKCYCLE project (risk-
based management of chemicals and products in a circular economy at a global
scale) are trying to assess the risks of these substances in a circular economy.
This second volume of the book presents the results obtained during the
RISKCYCLE project, paying special attention to a set of selected additives in the
diverse industrial sectors (i.e., PFOS, DEHP, Pb). Different methodologies have been
used to analyze aspects such as the fate, human and environmental exposure, and
toxicity of these compounds. Case studies have been developed to assess their risk in
developing countries such as China or Vietnam. The findings have been presented in
the different RISKCYCLE workshops as well as at the final conference in Dresden.
Finally, some research gaps have been identified which will provide the frame-
work for future work in the field of the chemicals and the environment.

Keywords Chemical risk, Environment, Global scale, Human health

D. Barceló
Department Environmental Chemistry, Institute of Environmental Diagnostic and Water Studies
(IDAEA), Spanish Council of Scientific Research (CSIC), Jordi Girona 18-26, 08034 Barcelona,
Spain
ICRA, Edifici H2O, Emili Grahit, 101, 17003 Girona, Spain
R.M. Darbra (*)
CERTEC, Department of Chemical Engineering, Universitat Politècnica de Catalunya, ETSEIB,
Diagonal 647, pav. G, 08028 Barcelona, Spain
e-mail: rm.darbra@upc.edu
B. Bilitewski, V. Grundmann and A. Zehm
Institut für Abfallwirtschaft und Altlasten, Technische Universität Dresden, Pratzschwitzer Str. 15,
01796 Pirna, Germany

B. Bilitewski et al. (eds.), Global Risk-Based Management of Chemical Additives II: 1
Risk-Based Assessment and Management Strategies, Hdb Env Chem (2013) 23: 1–4,
DOI 10.1007/698_2012_203, # Springer-Verlag Berlin Heidelberg 2012,
Published online: 24 November 2012
2 D. Barceló et al.

This book includes the results of a Coordination Action funded by the European
Union called RISKCYCLE (risk-based management of chemicals and products in a
circular economy at a global scale). This project (n. 226552) started the 1st of
September of 2009 and ended on the 31st of August 2012. Its main objective was to
establish and coordinate a global network of European and international experts and
stakeholders from worldwide countries (e.g., European countries, China, India,
Brazil, Vietnam) to assess the risks of hazardous chemicals and additives contained
in different daily products.
In order to accomplish with the aforementioned aim, during the first year of
project, an extensive research on the different chemical additives used in six
industrial sectors was conducted: plastics, textiles, electronics, lubricants, leather,
and paper. A list of selected chemical additives was identified for each sector and
used as a study basis for the rest of the project. This is the case of the decabromo-
diphenyl ether (BDE) used in electronics as a flame retardant or the triclosan used in
the textile as a biocide. The results of this investigation were presented in the first
volume of this book (Global Risk-Based Management of Chemical Additives I:
Production, Usage and Environmental Occurrence). This volume also included
a section of case studies related to the selected additives in different countries
(i.e., Denmark, Vietnam, Brazil, India). The main outcomes of the first part of the
project are summarized below:
• There exists a very wide range of chemical compounds used as additives in final
products.
• The role of the chemical additives in order to provide the final characteristics of
the products is essential.
• These additives can be applied during different stages during the product
production (e.g., manufacture, finishing process).
• At the end of the product’s life, the chemicals can be released into the environ-
ment with potential harmful effects to humans and ecosystems.
• Information regarding emission, fate, exposure, and toxicity of these chemicals
is scarce, especially at the end of the product’s life.
• Assessing the environmental risks associated with additives along the whole
product’s life cycle at a global scale is an issue of paramount relevance, which
requires the development of proper methodologies and effort to gather
information.
This last outcome was the starting point for the work to be done during the
second part of the project. At this point, the different work packages focused on
their topics, that is, in environmental fate, toxicology, risk assessment, life cycle
assessment, and socioeconomic issues. The objective was to apply the different
methodologies related to these fields of knowledge to the selected substances in
order to assess the potential risk that they can pose to the human health and the
environment.
In part I of this second volume, a review of these different methodologies has
been conducted. The potential benefits of the different models as well as the
drawbacks are analyzed in order to select the most suitable of them for the
Introduction 3

application to particular case studies. In addition, also in this part, some aspects
related to the chemicals regulations are also reviewed, especially those affecting the
European new chemicals legislation, such as REACH (regulation concerning the
Registration, Evaluation, Authorizations and Restriction of Chemicals). Some
socioeconomic aspects are also treated in relation to the need of chemicals for the
society.
On the other hand, in part II of this volume, a set of case studies are introduced.
The application of the selected methodologies inside each one of the foresaid
disciplines (e.g., risk assessment, life cycle assessment) to specific cases and
countries is presented here. The results of such application are discussed as well
as their reliability. Toxicological studies in Italy, risk assessment of electronic
waste in China, or disposal of bearing lamps in India are some examples of selected
scenarios.
All the data gathered during the RISKCYCLE project as well as the results have
been presented in the book but at the same time to different international events
such as the four international workshops organized by the RISKCYCLE project:
– 1st Riskcycle Workshop: Risk-based Management of Chemicals and Products in
a Circular Economy at a Global Scale. Hanoi (Vietnam), 3–6 May, 2010
– 2nd Riskcycle Workshop: Risk of Chemical Additives and Recycled Materials.
Shenyang (China), 15–19 November, 2010
– 3rd Riskcycle Workshop: Environmental and Health Risks of Chemical
Additives and Recycled Materials. Rio de Janeiro (Brazil), 2–6 May 2011
– 4th Riskcycle Workshop: Sustainable Waster Management. New Delhi (India),
12–13 October
In addition, the RISKCYCLE team also organized a conference in Dresden in
May 2012 where the main outcomes of the project were presented to and discussed
with the public. Apart from this, other dissemination activities have been carried
out during the project such as contributions to other conferences and workshops,
exchange of students, publications in scientific journals, and training courses on
different methodologies among the partners.
At the end of the project, a set of research gaps to be taken into consideration for
the future have been identified such as the lack of data about chemicals in products
as well as their emission to the environmental compartments, the need to assess the
risk of chemical mixtures and not the chemicals by themselves, or the necessity of
optimizing the current legislation on chemicals.
As it can be seen, after 3 years of research, several gaps have been identified and
showed the need to continue the research on the chemicals contained in products
and transported worldwide. This is the future aim of the RISKCYCLE consortium.
Part I
Methodologies for the Global
Management Strategies
Life Cycle Assessment of Additives:
Methodology and Data

Ester van der Voet, Lauran van Oers, Tomas Rydberg, Jenny Westerdahl,
and Henrik Fred Larsen

Abstract Life cycle assessment (LCA) is a useful tool to assess impacts of cradle-
to-grave chains of products/services. In the Riskcycle framework, the focus is on
additives. Additives are usually minor constituents of products, but depending on
their specific properties they can be important in the total scope of impacts of such
products. In the LCA literature, additives are hardly visible. Most case studies of
products containing additives do not mention them. The reasons for this are unclear,
but are at least partly due to the fact that information on additives is not included in
standard LCA databases. This is true for both life cycle inventory (LCI) and life
cycle impact assessment (LCIA) databases. Therefore, it is difficult to conclude
whether or not additives indeed are important contributors to environmental
impacts over the life cycle.
In the Riskcycle project, we have addressed these knowledge gaps for two
categories of materials: plastics and paper (printed matter). Case studies have
been conducted for products containing those materials (Larsen, 2012, Case study
on printed matter, Hdb Env Chem; van Oers and van der Voet, 2012, LCA case
study cushion vinyl floor covering and DEHP, Hdb Env Chem). A coherent attempt
has been made to derive LCIA factors for toxicity for a large number of plastics-
and paper-related additives (Åstr€ om et al., 2012, Are chemicals in products good or
bad for the society? – the economic perspective, Hdb Env Chem. doi:10.1007/
698_2012_184). In this chapter, we summarize and generalize these findings and
try to establish a coherent framework for LCA studies of products containing

E. van der Voet (*) and L. van Oers
Institute of Environmental Sciences, Faculty of Science, Leiden University, P.O.Box 9518,
2300 RA Leiden, The Netherlands
e-mail: voet@cml.leidenuniv.nl
T. Rydberg and J. Westerdahl
IVLSwedish Environmental Research Institute LTD, P.O.Box 21060, 10031 Stockholm, Sweden
H.F. Larsen
Danish Ministry of Transport, Road Directorate, Guldalderen 12, 2640 Hedehusene, Denmark

B. Bilitewski et al. (eds.), Global Risk-Based Management of Chemical Additives II: 7
Risk-Based Assessment and Management Strategies, Hdb Env Chem (2013) 23: 7–24,
DOI 10.1007/698_2012_185, # Springer-Verlag Berlin Heidelberg 2012,
Published online: 15 August 2012
8 E. van der Voet et al.

additives. In this framework, we distinguish three relevant levels that have to be
part of such LCA studies: the product level, the material level and the additive level.
We also establish the relation of LCA toxicity assessments with risk-based
approaches.

Keywords Additives, Life Cycle Assessment, LCI data, LCIA data, Plastics,
Paper
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2 Life Cycle Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3 LCA and Additives in Plastics and Printed Matter/Paper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.1 Plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2 Printed Matter/Paper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4 Approach Taken in Case Studies to Estimate Missing Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.1 LCI Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.2 LCIA Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
5 Approaches to Improve LCA Studies with Respect to Additives . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5.1 Method Issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5.2 LCI of Additive Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
5.3 Towards a Harmonized Approach for LCAs of Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

1 Introduction

Additives form a part of the life cycle of many materials and therefore many
products, wherein the materials are applied. Additives sometimes pose a risk to
human and environmental health. Therefore, it may be expected that in life cycle
assessment (LCA) studies this will show.
van Oers and van der Voet [1] did a literature review on published LCA case
studies on plastics and additives, with the purpose of establishing the importance of
additives in the life cycle of plastics and plastic products. To their surprise, they
found that additives are not often even mentioned in LCA case studies. The
literature survey resulted in 110 LCA case studies of plastics and plastic products.
In about 25 of those, additives are mentioned. In none of the articles, the plastic
additives are mentioned as an important issue in the life cycle impacts of plastics.
For printed matter/paper the overall picture is about the same as described by
Larsen [2] in this volume on printed matter case studies.
The reason for this apparent lack of importance regarding additives in LCAs is
not obvious. Speculation leads to various possibilities:
• Additives do not contribute significantly to the life cycle impacts of plastics and
paper products, and therefore do not come out in the results.
• Life cycle inventory (LCI) data on additives may be incomplete.
• The life cycle impact assessment (LCIA) may be restricted to one or a few
impact categories, where additives do not contribute much.
• Life cycle impact characterization factors may be missing for a lot of additives.
Life Cycle Assessment of Additives: Methodology and Data 9

Those possible explanations are investigated in this chapter. We will shortly
describe the LCA methodology in Sect. 2. We will review case studies on plastics
and printed matter/paper in Sect. 3. In Sect. 4 we will address the data situation for
LCI databases and LCIA characterization factors. In Sect. 5 we will come to some
conclusions and recommendations.

2 Life Cycle Assessment

LCA is a methodology out of the Industrial Ecology toolbox. It is designed to
specify and compare the environmental impacts of cradle-to-grave chains of
products or services. It is standardized by ISO [3] and has the following methodo-
logical steps:
1. Goal and scope definition, where the goal of the study is defined, the eventual
alternatives that will be considered are given, the system boundary is determined
and the processes within the product- or service-system are defined.
2. LCI, where the system is quantified in a strict format of linked processes. Each
process is described in terms of the physical inputs and outputs, both economic
(raw materials, materials, products) and environmental (extractions from and
emissions to the environment). Out of the total, an ecological profile is compiled
listing and adding up all extractions and emissions of the system. An important
methodological issue is allocation: how to deal with multi-output processes?
This issue is especially important when dealing with waste management pro-
cesses and will be dealt with below.
3. LCIA, where the ecological profile is translated into a number of impact
categories. These can be defined at “midpoint” level (acidification, toxicity,
global warming, land use) or at “endpoint” level (human health, ecosystem
health). Here, the main debate is on how to translate individual emissions and
extractions into impact potentials for the different impact categories. For
additives, the toxicity-related impact categories are important and also belong
to the most difficult and controversial ones.
4. Interpretation of the results, which includes both the evaluation of the results in
terms of the goal and scope as defined before and the assessment of the
robustness of the results in terms of uncertainties and data gaps.
Coming back to the question of why additives do not show up in LCA case
studies, this may be linked now with the various steps in the LCA procedure,
especially to the LCI and the LCIA.
In the LCI, we have to rely on databases that are more or less incomplete. In
general, production data are best covered, but even there may be gaps. Data on
consumption and use processes are scarce in general – for additives, these use
processes may be important since additives may leach out or evaporate from
products in use. On waste treatment the data situation is also not very good.
Average waste treatment processes out of LCI databases are not usable – these
describe emissions out of municipal waste treatment in general. Sometimes specific
10 E. van der Voet et al.

processes or spreadsheet calculators are added for materials, such as plastics or
paper, but whether additives are recognizable in them is to be doubted.
Another LCI-related issue is allocation. This is especially relevant to waste
treatment options: when waste is recycled or used to generate energy, there is a
multi-output process which needs to be dealt with. The waste then is no longer
considered a waste, but a resource, and waste treatment is becoming a production
process as well. What part of the emissions to allocate to the waste treatment service
and what part to the secondary material or other co-product is then open to debate.
ISO allows for various options. Whether additives are even visible in such pro-
cesses is, again, doubtful.
In LCIA, emissions are translated into impact potentials for several impact
categories. Additives may be expected to contribute to toxicity impact categories.
Toxicity, however, is a complicated category with a great many specific substances
contributing to it via a great many different pathways and mechanisms. In the LCA
community, this is very much a category in development, and for a great many
substances, such impact factors are still missing. This may also contribute to the
invisibility of additives.
In the next section, we will investigate for two materials, plastics and paper,
which possible explanations are correct for the invisibility of additives in LCA case
studies.

3 LCA and Additives in Plastics and Printed Matter/Paper

In Sect. 3.1, we will address plastics, and in Sect. 3.2 printed matter/paper. Based on
the literature and on our own work we will try to identify causes of the absence of
additives.

3.1 Plastics

3.1.1 LCI Data

Van Oers et al. [4] conducted a review of over 30 LCI databases to assess the data
situation on additive production and use. They came to the following conclusions:
• Data on additive production are mostly absent in LCI databases. Some data are
available for metals production and for bisphenol-A, but even for widely used
additives such as phthalates and brominated flame retardants, production data
are not available.
• Data on plastic resins and the conversion of resins into materials or (half)
products are present in most databases. Surprisingly, these data do not include
additives. Neither the (compound) plastics nor the conversion processes take the
inclusion, and thus possible emissions, of additives into account. Even more
disturbing is that this is not clear to users of the database, which lead to the
Life Cycle Assessment of Additives: Methodology and Data 11

suspicion that LCA case studies on plastics or plastic products have been
performed without authors realizing additives are not included.
• No LCI data for the use of plastics and plastic products are available.
• In some databases, material-specific data are present for various waste treatment
options. Plastics generally are among the materials included. However, no
specific data on additives are found. In case of incineration, organic additives
break down and therefore are not expected. In case of landfill, some leaching of
evaporation would be probable, but cannot be found in the data.
• Data on plastics recycling are very poor.
In all, it would appear that including additives in LCA case studies on plastic(s)
(products) is not possible by using standard LCI databases. Specific efforts must be
made to supplement missing data in all stages of the life cycle.

3.1.2 LCIA Data

The data situation for additives in LCIA seems to be somewhat better than for the
LCI [4]. Characterization factors exist for a number of additives and for a number of
impact categories. Nevertheless, the list is nowhere near complete. Especially for
the impact categories of human toxicity and ecotoxicity, impact factors are missing.
Approaches exist to calculate such factors based on substance characteristics. In
this volume, LCIA factors are derived for a large number of additives based on such
approaches [5]. The lack of such factors, therefore, seems to be less of a problem for
including additives in LCA case studies than the lack of LCI data.

3.1.3 LCA Case Studies

As mentioned before, additives do not come out as contributing to life cycle
impacts in any of the 110 case studies reviewed. From the above, it is clear that a
straightforward LCA case study using a standard LCI database would indeed not
show additives, because they are not present in these databases. The fact that the
plastics data are aggregate data masks any omissions, implying it is possible that
case study performers were unaware of it. For example the studies on (waste
treatment) of plastic packaging [6–12], plastic cup studies [13, 14] and some studies
on automotive parts [15, 16] do not mention additives at all.
About a quarter of all papers do include additives, mostly phthalates (DEHP), but
also pigments (TiO2), and stabilizers (lead). These are mainly articles about devel-
oping LCIA impact assessment factors, not case studies. Of the case studies, only the
comparative LCAs of flooring and window frames, and a few of the LCAs of the
waste treatment options mention additives. However, for the latter most articles only
give qualitative information on additives. In the LCAs about PVC containing
flooring ([17, 18, 39]) and window frames [19] the production of additives is taken
into account. However, only Potting and Blok [18] and Asif et al. [19] also refer to
emissions of additives, like DEHP and lead stabilizers. In their papers, additives do
not appear to contribute to life cycle impacts.
12 E. van der Voet et al.

To test the assumption whether additives indeed do not contribute to any
significant amount to life cycle impacts of plastics, Van Oers and Van der Voet
[1] conducted a case study on PVC flooring, appearing in this volume as well. They
conclude that additives can indeed contribute to life cycle impacts, and therefore
more attention should be paid to additives. Closing the data gaps therefore seems to
be a very important issue.

3.2 Printed Matter/Paper

For printed matter/paper we see about the same picture as for plastics but the
number of case studies is far less.

3.2.1 LCI Data

Besides additives like phthalates and bisphenol-A mentioned for plastics, but also
used in printing inks, other additives like pigments, siccatives and biocides also
miss usefull inventory data to a high degree. As described by Larsen [2], a review of
the relatively few existing case studies on printed matter shows that inventory data
on additives are missing to a high degree. That this kind of data are difficult to find
in existing databases is confirmed by a running case study on printed matter/paper
performed at DTU (part of the EU project LC-Impact). In this ongoing project it
has, however, been possible to find LCI data on a few additives like alkyd resin and
kaolin, but only for carbon black as regards pigments. Looking at recycling of
paper, which is of special focus in RiskCycle, recent ongoing research on additives/
impurities in food packaging based on recycled paper [20, 21] could contribute with
valuable LCI data in future case studies.

3.2.2 LCIA Data

As regards LCIA of additives the toxicity-related impact categories, i.e. ecotoxicity
and human toxicity, are important. In order to quantify the potential (eco)toxic
impacts of additives the emitted amount and a characterization factor (impact
potential per kg emitted) for each is needed. As described above data on emissions,
being part of the LCI data, are missing to a high degree. For characterization factors
the picture is slightly better due to newer LCIA models like USEtox covering more
than 2,000 substances, and specific initiatives on calculating characterization
factors for additives in printed matter like in Larsen et al. [22]. Anyway, most of
these factors have a low quality (are interim) due to lack of good and sufficient fate
and effect data on which they are depend.

3.2.3 LCA Case Studies

As described by Larsen [2] only about ten case studies on printed matter (including
paper) have been reported so far and almost all of them focus on energy
Life Cycle Assessment of Additives: Methodology and Data 13

consumption and do not include additives at all, or only to a very limited degree.
Even a most recent Finish LCA study on different printing technologies [23] focus
on energy (and material) consumption and only includes toxicity-related impact
categories (i.e. human toxicity, terrestrial ecotoxicity and freshwater ecotoxicity)
for the case study on a photobook (electrophotography/digital printing). The LCIA
method used in this case is one of the newest, i.e. ReCiPe (www.lcia-recipe.net
(version November 2009)) but the study only includes cradle to consumer (no “end
of life” or recycling included). The resulting LCA impact profiles in the Finish case
study shows dominance of the paper production together with the packaging
material (plastic) for the photobook and transport to the consumer. Regarding the
toxicity-related impact categories only the normalized impact potential for “Fresh-
water ecotoxicity” is significant and mainly related to metal emissions from plastic
production. No other contribution from emissions of chemicals used (e.g. additives)
are mentioned in the study, which is probably due to the general lack of inventory
data and lack of characterization factors for toxicity contributing chemical
emissions in available LCA databases.
Anyway, one of the recent and most comprehensive LCA studies on printed matter
[22, 24] focus on the importance of chemical emissions as compared to emissions
related to energy, and actually include toxic impacts from chemical emissions like
printing ink, of which some components may accumulate in recycled paper.
The results of this case study shows that paper production contribute signifi-
cantly (about 30% of total) to the impact profile but is not at all dominating like in
former studies (60–80% of total) focusing on energy consumption and only includ-
ing chemicals/additives and potential toxic impacts to a limited degree. Even
though recycling of paper is included in this study there is no special focus on the
additives/impurities in the recycled paper. However, the study shows that potential
toxic impacts from the production and use of chemicals like pigments, solvents,
metals, AOX and biocides may play a very significant role in the impact profile of
printed matter. As for plastics, it therefore seems most probable that the inclusion of
potential (eco)toxic impacts from additives/impurities could change future impact
profiles of printed matter/paper case studies strongly. Filling the data gap on LCI
and characterization factors regarding printed matter and paper-related additives is
therefore highly relevant for the future possibilities to significantly improve the
comprehensiveness and reliability of case studies on printed matter/paper.

4 Approach Taken in Case Studies to Estimate Missing Data

4.1 LCI Data

4.1.1 Plastics

In the case study on PVC flooring, process descriptions are based on the Ecoinvent
database, version 2.2 [37]. Production data for DEHP are missing and are added,
14 E. van der Voet et al.

based on data from Potting and Blok [18] and processes from the ecoinvent
database. Process descriptions for the production of stabilizers and other materials
are missing as well, but are not further elaborated. In the ecoinvent database also
emissions of DEHP are lacking. Therefore additional estimates for the emission of
DEHP during production, use and waste disposal are estimated, based on several
MFA studies ([25–27, 38]).
Waste treatment technologies for incineration and landfill of PVC are present in
the ecoinvent database. The material specific burdens for the waste treatment are
calculated by a supporting spreadsheet. Necessary data for the calculation of the
burden are, e.g. element composition, water content, energy content, degradability
in landfill, etc. Note that the Ecoinvent waste management model estimates
emissions based on the element composition and some general characteristics of
the materials (like degradability). Detailed characteristics, like the mobility of
DEHP from PVC, are not taken into account. Therefore additional assumptions
have been made for the emission of DEHP from landfill of PVC.
In the earlier mentioned MFA studies, no direct emission of DEHP from waste
incineration or landfill to air or surface water is reported. For incineration it is
assumed that DEHP is decomposed into CO2 and H2O. For landfill it is assumed
that DEHP is degraded into CO2 and CH4 [26] or enters the waste water, which
subsequently is treated in the WWTP [27].
The above described landfill refers to a highly controlled landfill site with
emission precaution measures. For less-controlled landfill sites, DEHP emissions
will probably occur and should be estimated accordingly. The evaporation factors
used for estimating emissions in the use phase are used for landfill sites as well, as a
crude first estimate [1].
Since no data on recycling processes are available, estimates had to be made in
addition as well, described by Åstr€ om et al. [5].
The conclusion from this exercise is that although data are missing to a large
extent, it is possible based on the literature and some educated assumptions to come
up with reasonable estimates. In the absence of real data, such an approach is
preferable to ignoring additives altogether, since they can contribute to impacts
significantly.

4.1.2 Paper

In the case study on sheet-fed offset printed matter described by Larsen [2],
emission data related to chemicals including additives are only to a limited degree
taken from LCA databases. This is due to the fact that LCI data on printing
production is almost generally missing in available databases. Most of the non-
energy-related emissions are therefore based on measured and estimated emissions
from 10 to 71 Scandinavian printing houses including litterature values and
estimates based on mass balances taking physical/chemical substance properties
into account to some degree. Both recycling, incineration and landfill (in a sensi-
tivity analysis) of printed matter are included in this case study but potential impact
Life Cycle Assessment of Additives: Methodology and Data 15

of additives/impurites in the recycled paper is not included due to lack of relevant
data. As mentioned above ongoing research on additives/impurities in food pack-
aging based on recycled paper [20, 21] might make it possible to include these
potential impacts in future case studies on printed matter/recycled paper.
As part of the case study described by Larsen, a generic sheet-fed offset printing
ink composition (about 12 components) is created based on input from former
active managers of ink production, a search in the Danish Product Register, a
literature search and information from several suppliers/producers/knowledge
centers within the printing industry. Based on former investigations at printing
houses and a literature search it is assumed that 1% is emitted via wastewater, 20%
ends up as chemical waste (hazardous waste) and about 80% stays on the paper.
Looking at pigments, being one of the essential components in printing ink, the
potential impact from their production has been estimated. For the azo-pigment
Pigment Yellow 14 (diarylamide) and the phthalocyanine pigment Pigment Blue
15, both types highly used in printing inks, the emitted amount is based on estimates
by Andersen and Nikolajsen [28].The estimations by Andersen and Nikolajsen are
done using lowest values on emitted amounts from the EU Technical Guidance
Document on risk assessment assuming wastewater treatment at the production
facilities. For Pigment Yellow14 the main contributing emissions are water
emissions of 3,3-dichlorobenzidine and 2-chloroaniline during the synthesis of
the pigment. For Pigment Blue 15 the main contributor is water emisssions of
cuprous chloride also during synthesis. Unfortunately, it has not been possible to
include potential impacts of pigments in the recycling process and as impurities in
recycled paper, due to lack of data.
In the ongoing printed matter case study related to the EU FP7 project LC-
Impact the EcoInvent v. 2.2 unit processes on graphic paper, which seems to be the
most comprehensive avaliable database, are going to be included. Even though
these unit proceses include recycling and deinking of paper, very few of the
chemical emissions related to the problematic on additives in paper are included
and emissions of additives/impurities in recycled paper are not included at all. For
the production of printing inks the plan is to use the EcoInvent v. 2.2 unit process on
“printing colour, offset, 47.5% solvent at plant” but only as a starting point. In this
database process organic pigments are substituted by polyethylene terephthalate
and the only other components included are carbon black, binders (alkyd resin,
bitumen, soya oil, palm oil), solvents (substituted by light fuel oil) and filler
(limestone). So, typical components of offset printing inks are highly substituted
or non-occuring like siccatives, antioxidants and litho additives (e.g. EDTA).
Chemical emissions are therefore missing to a high degree in this unit process,
but even though it is probably the best existing one. However, one should be aware
that while it might be used as a proxy for the energy and infrastructure of printing
ink production, it is no good for the emissions (of precursors, metabolites, etc.)
directly related to the production of many printing ink components like the
dominating azo-pigments and phthalocyanine pigments. Here an approach like
the one by Andersen and Nikolajsen [28] might be used.
16 E. van der Voet et al.

4.2 LCIA Data

Missing LCIA data have been supplemented by impact factors calculated with
USEtox™.
As mentioned above, there are characterization factors for a number of different
impact categories, e.g. acidification, eutrophication, climate change, human toxic-
ity and ecotoxicity. However, characterization factors are missing for many
additives, especially for human toxicity and ecotoxicity, which makes it difficult
to assess the potential impact that a product will cause during its entire life cycle. A
major reason that characterization factors are often missing is the lack of data
regarding substance properties, such as physical chemical properties and toxicity.
One method of deriving characterization factors for additives with regard to
human toxicity and ecotoxicity is by using the LCIA model USEtox™ [29]. Based
on the physical chemical properties and toxicity of the substance, USEtox™
calculates characterization factors for both human toxicity and aquatic ecotoxicity.
According to the USEtox™ manual [29], preference should be given to experimen-
tal values when deriving characterization factors with USEtox. However, the lack
of experimental data is often the reason that characterization factors are missing.
Experimental tests are often both expensive and time consuming to perform. Thus
there is a need to be able to generate these data by the use of other methods.
In a study by Andersson et al. [30], the possibilities to use quantitative structure-
activity relationship (QSAR) models to predict physical chemical and ecotoxico-
logical properties of approximately 200 different plastic additives have been
assessed. Physical chemical properties were predicted with the U.S. Environmental
Protection Agency Estimation Program Interface (EPI) Suite, Version 3.20.
Aquatic ecotoxicity data were calculated by QSAR models in the Toxicity Estima-
tion Software Tool (T.E.S.T.), version 3.3, from U.S. Environmental Protection
Agency, as described by Rahmberg et al. [31]. To evaluate the applicability of the
QSAR-based characterization factors, they were compared to experiment-based
characterization factors for the same substances taken from the USEtox™ organics
database [32]. This was done for 39 plastic additives for which experiment-based
characterization factors were already available.
In a first attempt to derive characterization factors with QSARs, the entire
dataset of plastics additives was included, and aquatic ecotoxicity was predicted
for two different trophic levels. This generated characterization factors that did not
correspond well with the ones derived from experimental data [30]. Hardly
surprising, but a clear indication that two trophic levels are unsufficient. A second
attempt to derive characterization factors with QSARs are currently being
performed [31]. In this second attempt, substances that are difficult to model in
QSAR models have been removed from the dataset and the ecotoxicity has been
predicted for three different trophic levels instead of two. However, results have not
yet been obtained from this second attempt. If the results show that it is possible to
derive reliable characterization factors by the use of QSARs, the current data gap
regarding characterization factors for human toxicity and ecotoxicity could be
Life Cycle Assessment of Additives: Methodology and Data 17

reduced, even though, with present knowledge, QSAR-based characterization
factors are to be considered as interim.

5 Approaches to Improve LCA Studies with Respect
to Additives

There are both data issues, and methodological issues to deal with when assessing
additives in LCA.

5.1 Method Issues

Additives are part of materials, and materials are used in products. That means that
for LCA case studies three life cycles have to be kept in mind:
• The life cycle of the product, which is the usual entrance in an LCA.
• The life cycle of the material, which can be different from that of the product.
Materials are produced and have a functional use in a product, after the products
life span the materials may be recycled to enter another life cycle, possibly in
another product.
• The life cycle of the additive, which in turn can be different from that of the
material additives are produced and then have a functional use in a material.
They follow the life cycle of the material but may disappear from it during the
use phase or in landfill, and when incinerated or recycled may end up in different
streams. Methodologically speaking this may be the biggest challenge: besides
the challenge of mapping its fate, when to consider a material/additive as a
resource and not as a waste?
As the collective LCA studies on plastics show, these three life cycles have in
many cases not been respected. The LCA framework does not force the user to do
so. In order to do that, additional tools may have to be used, especially Material
Flow Analysis.
Another methodological issue, although of a different nature, is allocation.
Especially in waste management processes, allocation is problematic, while at the
same time it can influence the LCA outcomes significantly. In case of landfill,
things are straightforward: the end of all three life cycles. In case of incineration it
can be an issue when energy is generated from the incineration process. Then the
process delivers two services, waste treatment and energy generation, over which
the emissions must be divided. This is not specific for additives, though. In case of
recycling, the process delivers a waste treatment service while at the same time
producing secondary materials. Here, it is interesting to regard additives: do they
disappear in the process, do they end up in a waste stream, are they recovered
somehow, or are they also present in the secondary material? This makes a
difference, also in how to allocate.
18 E. van der Voet et al.

5.2 LCI of Additive Production

As was pointed out in the case study on plastics above, little attention has been
given to additives in products in LCAs and therefore the available information on
production of additives is very limited. Thus, there is a need to include production
of additives in the LCI-databases to make LCAs more complete. To obtain these
data, cooperation with relevant industry is needed.

5.2.1 Emissions from Compounding and Product Manufacturing Processes

Information regarding emissions of additives during compounding and product
manufacturing can often be found in the Organisation for Economic Co-operation
and Developments (OECDs) Emission Scenario Documents (ESDs) [33]. These
documents describe emission processes and exposure scenrios for different indus-
trial sectors. In the ESDs, emissions are described on a general level, for example
emission factors are given for an entire group of substances and a certain industrial
process. These emission factors are often conservative in order to safeguard the
health of humans and other organisms that are exposed. Other possible sources of
information are risk assessments and MFAs/SFAs. One example where SFAs have
been used to track emissions is the Control of hazardous substances in the Baltic
Sea region (COHIBA) project, where SFAs were conducted for 11 hazardous
substances in the Baltic Sea area [34].

5.2.2 Emissions During Use

The ESDs developed by the OECD also include estimates of emissions of additives
during use. As for the emissions during compounding and product manufacturing,
these emissions are often conservative estimates based on rough models that give an
overview of the emissions from the products produced by an entire industry sector.
Emissions during use has also been quantified in the research programme
ChEmiTecs – organic chemical emitted from technosphere articles. Within the
research programme, emissions during use have been quantified by both
measurements in emission chamber and by the use of modelling [35]. The
modelling approach focussed on two different levels, one model describing
emissions on a molecular level [35] and one model that describes emissions of
organic substances on a national level [36].
This type of emission estimates can be included in LCAs to make them more
complete.

5.2.3 Emissions from Waste Management Processes

As stated earlier, in general data on emissions of additives from waste processes are
scarce.
Life Cycle Assessment of Additives: Methodology and Data 19

Landfill

Worldwide, most waste is landfilled. Emissions from landfill occur via evaporation
and leaching. Landfill sites can be managed to reduce those emissions, but in many
cases they are not. Data on leaching and evaporation of additives from landfill sites
are scarce.

Incineration

Organic compounds are degraded during incineration and converted to compounds
such as CO2 and H2O. Sometimes, pollutants such as dioxins are formed during
incineration processes, leading to toxic emissions to the atmosphere. Inorganic
compounds, in the case of additives usually metals, are not degraded. In well-
managed incineration plants, they end up in waste streams such as slag and bottom
ash. Re-use of such waste streams may lead to leaching of metals, depending on the
use and on the state of immobilization of the metals.

Recycling

Additives often form a problem in recycling processes. Material recycling is often
not possible or only with a considerable loss of quality. Plastics recycling is
notoriously difficult due to the mixed composition of the plastics waste stream.
The recycled material can only be used in certain applications that do not demand a
pure material. Recycling of the additives themselves is theoretically possible only
for metals, but in practice this type of recycling is not feasible. The metals occur
only in low concentrations. Recovery from fly ash and bottom ash is possible, but
expensive: in view of growing scarcity problems it may become a viable options for
at least some metals.

5.3 Towards a Harmonized Approach for LCAs of Additives

5.3.1 Conclusions

Additives are badly represented in LCA case studies. This is not because they do
not contribute to impacts, but because they are not included in the assessment. The
most likely reason for that is that specific LCI data for additives are missing to a
large extent, and additive data are not included in the compound materials. More-
over, this fact is not obvious. Possibly, LCA practicioners are not aware of this gap.
Additive data for the use phase and waste treatment phase are lacking as well. LCIA
data for additives are also lacking. Approaches exist, however, to estimate interim
characterization factors based on substance characteristics.
Additives can have a significant impact in a products life cycle as shown by the
case studies on plastics and printed matter/paper. Omitting them can therefore be
20 E. van der Voet et al.

crucial for the outcome of an LCA study. Not only for LCIA factors, but also for
LCI data, approaches can be developed to use in case of lacking data. Such an
approach is outlined below.

5.3.2 A Harmonized Approach

The approached outlined refers to the LCI, since they are the largest and most
prohibitive gaps.
• Data on additive production: if such data are missing, they must be collected,
there is no way around that. In some cases, however, proxy energy consumption
and proxy emission data may be estimated if the synthesis way and the default
emission factors for the technology used are known.
• Data on material production: the composition of materials is relatively easy to
obtain information. Hence it follows how much additive is needed. In the
process of producing the material, emissions of additives take place. MFA
studies exist that provide estimates of such emissions, based on inputs and
outputs of processes. These studies refer to a specific situation in a country.
An attempt can be made to modify them for different situations. If this is not
possible, it is always better to use the existing data as a first rough estimate than
not to do so.
• Data on the production of products from the materials: these cannot be missing
from the LCA study. What may be missing is an estimate of emissions of
additives during that process. Emissions can be expected to be typically a lot
lower than for the material production, however.
• Data on the use phase: during use of the product, additives may leach out. Here,
too, emission factors may be derived from MFA studies or from the literature in
general.
• Data on the waste management phase: those are really difficult to obtain.
Measurements of additive emissions are scarce. Material specific emissions
data are always modelled. Estimates can only be based on rough assumptions.
Especially in cases of unprotected landfills, the leaching from landfill sites may
be important: here, too, it is better to use crude estimates than nothing at all.
Assumptions on emission rates together with an assumed time horizon should be
made.

5.3.3 Recommendations

A first recommendation is to take additives seriously as a part of the life cycle, at
least for plastics and printed matter/paper.
A second recommendation is to complete LCI databases with data on additives.
Both production data of additives and emission data of additives from compound
materials in the use and waste phase are missing and should be supplemented. An
important role in this data remediation process should be played by industry.
Life Cycle Assessment of Additives: Methodology and Data 21

A third recommendation is to expand LCI databases with data on various waste
treatment process in a material specific way. This is especially applicable to
recycling processes.
A fourth recommendation is to expand LCIA databases with characterization
factors on additives. Ideally this should be done on the basis of measured physical/
chemical and effect data but even interim characterization factors based on sound
QSAR estimations are better than none.
Finally, it is generally recommended to use estimation approaches, combined
with sensitivity analysis, for additives when data are missing, when performing an
LCA case study on additive containing products, such as outlined above. Only
when they are included it is possible to draw conclusions on the importance of
additives over the life cycle of a product.

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Characterization of Environmental Exposure:
Measuring Versus Modeling

Daniel Guillén, Antoni Ginebreda, Rosa M. Darbra, Meritxell Gros,
Mira Petrovic, and Damià Barceló

Abstract Knowledge of pollutants’ occurrence in the environment is essential in
order to undertake accurate risk assessment studies. Determining the concentration
of chemicals is a crucial step to quantify the levels to which both ecosystems and
human population can be exposed. Traditionally, analysis has been the main way for
determining concentrations in the environment but in recent years innovative occur-
rence models enabling their prediction either in real or fictitious scenarios have been
developed. These models allow obtaining reliable estimations by reducing the need
of resource-intensive monitoring programs that are needed for laboratory analysis.

D. Guillén (*) and A. Ginebreda
Department Environmental Chemistry, Institute of Environmental Diagnostic and Water Studies
(IDAEA), Spanish Council of Scientific Research (CSIC), Jordi Girona 18-26, 08034 Barcelona,
Spain
e-mail: danigui84@gmail.com
R.M. Darbra
CERTEC, Department of Chemical Engineering, Universitat Politècnica de Catalunya, ETSEIB,
Diagonal 647, pav. G, 08028 Barcelona, Spain
M. Gros
ICRA, Edifici H2O, Emili Grahit, 101, 17003 Girona, Spain
M. Petrovic
ICRA, Edifici H2O, Emili Grahit, 101, 17003 Girona, Spain
ICREA, Passeig Lluı́s Companys, 23, 08010 Barcelona, Spain
D. Barceló
Department Environmental Chemistry, Institute of Environmental Diagnostic and Water Studies
(IDAEA), Spanish Council of Scientific Research (CSIC), Jordi Girona 18-26, 08034 Barcelona,
Spain
ICRA, Edifici H2O, Emili Grahit, 101, 17003 Girona, Spain

B. Bilitewski et al. (eds.), Global Risk-Based Management of Chemical Additives II: 25
Risk-Based Assessment and Management Strategies, Hdb Env Chem (2013) 23: 25–46,
DOI 10.1007/698_2012_190, # Springer-Verlag Berlin Heidelberg 2012,
Published online: 31 August 2012
26 D. Guillén et al.

Prediction of chemical occurrence is a difficult task that depends on multitude of
factors (i.e., physical–chemical properties, climate conditions, amount of product,
mode of application, and exchange processes), but these models in combination with
laboratory analysis can be a powerful tool for evaluating the chemical occurrence in
the environment.
In this chapter the new trends in analytical chemistry for determining classical
and emerging pollutants, as well as the use of predictive exposure models have been
reviewed and their respective benefits and shortcomings have been briefly
discussed.

Keywords Analytical chemistry, Environmental concentration, Measuring,
Modelling, Risk assessment

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2 Exposure Assessment: Experimental Measuring or Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3 New Trends in Analytical Chemistry for Measuring Environmental Concentrations . . . . . 31
4 Predicting Environmental Concentrations Through Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
5 Future Challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

Abbreviations

CNT Carbon nanotubes
DBPs Disinfection by-products
EINECS The European inventory of existing commercial chemical substances
GC Gas chromatography
GCxGC Two-dimensional gas chromatography
GIS Geographic information system
IDA Information-dependent acquisition
KOC Organic carbon partition coefficient
KOW Octanol-water partition coefficient
LC Liquid chromatography
LOD Limit of detection
MAE Microwave-assisted extraction
MEC Measured environmental concentration
MS Mass spectrometry
MS/MS Tandem mass spectrometry
PAHs Polyaromatic hydrocarbons
PCBs Polychlorinated biphenyls
PEC Predicted environmental concentration
PFCs Perfluorinated compounds
POCIS Oolar organic chemical integrative samplers
Characterization of Environmental Exposure: Measuring Versus Modeling 27

QqLIT Hybrid quadrupole linear ion trap
QqTOF Hybrid quadrupole time-of-flight
QSAR Quantitative structure–activity relationship
REACH Registration, evaluation, and authorization of chemicals
SFE Supercritical fluid extraction
SPME Solid phase micro extraction
SRM Selected reaction monitoring
ToF Time-of-flight
TWA Time-weighted average
UPLC Ultra high performance liquid chromatography
UV Ultraviolet

1 Introduction

One may reasonably estimate that about 100,000 synthetic chemicals are currently
utilized by our technological society, of which 30,000–70,000 are of common
daily use (EINECS inventory) [1]. Furthermore, worldwide chemical production is
expected to extensively grow in the next decades. As a consequence of the human
activity many of these organic and inorganic compounds together with their degra-
dation products may ultimately enter the environment as a consequence of human
activity. Once they reach the environment, depending on their physical–chemical
properties, partitioning between the different environmental compartments (air, soil,
water, sediments, etc.) can also take place. In addition, many compounds may
undergo transformation processes giving rise to the corresponding metabolites or
degradation products. The result is a potential exposure to a cocktail of contaminants
whose environmental and health effects in short and long term are unpredictable.
This intensive growth has led to the need to enhance the international assessment
of chemical risks and strengthen the national and international regulatory efforts for
the proper management of chemicals. In this context, the existing European regula-
tion REACH (Registration, Evaluation, Authorisation of Chemicals) (EC 1907/
2006) [2] promotes the regulation of the chemicals used in commerce and consumer
products and the evaluation of the risk of human or environmental exposure to these
chemical compounds as well.
Risk assessment constitutes a cornerstone for the control of chemicals for both
scientific and management purposes. Environmental risk management deals with
regulatory measures based on risk assessment [3]. Strategies such as the prioritiza-
tion of chemicals represent a useful tool to optimize efforts for both regulatory and
monitoring purposes [4, 5].
The analysis of chemical risk is a process comprising the following elements:
hazard identification, exposure assessment, dose–response assessment, and risk
characterization [6]. Figure 1 shows the main elements that constitute the risk
characterization process together the methodologies used for their determination.
The essence of risk characterization is to relate the exposure (the concentration of a
28 D. Guillén et al.

Hazard identification

Exposure Effects
Analytical methods for
Models for predicting
the determination of In vivo/In vitro QSAR models
environmental
environmental assays In silico methods
Concentrations (PEC)
concentrations (MEC)

Risk characterization

Fig. 1 Risk characterization of chemicals: main methodological steps for determining their
exposure and effects. Adapted from [7]

chemical substance or mixture) with effects (the relationship between dose and the
associated impairment caused on organisms) to provide a scientific basis for
evaluating risks to both the environment and the human health.
The exposure assessment stage is crucial and consists of quantifying the level of
chemicals to which populations, population subgroups, and individuals are
exposed, in terms of magnitude, duration, and frequency [8]. In this chapter both
modelling and measuring procedures that are currently used for determining envi-
ronmental concentrations are briefly discussed.
Measuring is certainly the preferred method for quantifying concentrations of
chemicals (organic and inorganic) in environmental matrices. However laboratory
measurements are costly and time-consuming processes requiring intensive efforts:
field sampling campaigns, development and validation of analytical methodology,
thorough treatment of data, etc.
On the other hand, indirect methods should be considered as an alternative when
analytical measurements are not feasible. Predicting methods involve extrapolating
exposure estimates from existing data, e.g., previous environmental monitoring,
data about emissions and chemicals production, and questionnaires. Distribution of
chemicals among the different environment compartments is also a key aspect for
predicting environmental concentrations. Therefore psysicochemical properties
(see Sect. 4) are required inputs in these tools.

2 Exposure Assessment: Experimental Measuring or Modeling

As mentioned before, environmental exposure is the first key aspect to develop risk
characterization from a defined scenario (see Fig. 1). Experimental analysis is the
most obvious and classical procedure for determining the chemical occurrence in the
environment. Measuring environmental concentrations (MECs) is more accurate
and reflects the reality better than any other method, but the main drawback is
the large amount of resources required for these laboratory measurements. Field
environmental monitoring programs have become increasingly expensive as
Characterization of Environmental Exposure: Measuring Versus Modeling 29

a consequence of constantly rising environmental quality criteria, the elevated
number of environmental matrices (surface waters, ground waters, soils, sediments,
biota, air, etc.) and the necessity to determine concentrations of pollutants at
extremely low concentrations (ng/L). It means that monitoring programs may
become highly time consuming and thus very costly; hence monitoring campaigns
are not always a feasible procedure since it is not possible to have a full coverage of
time and space. Nonetheless environmental studies based on experimental
determinations are highly time consuming and require great laboratory facilities
and human resources (qualified personnel and expensive equipments).
An interesting alternative to experimental measurements is modeling, which
allows estimating environmental concentrations through appropriate calculations
derived from some input data and reliable and well-established physical–chemical
principles (usually referred as PEC or Predicted Environmental Concentrations).
Modeling is fast and relatively affordable and has very good time and space
coverage possibilities, being, on the other hand, its main weakness the strong
dependence on the model chosen and its inherent uncertainty because of the lack
of reliable data (production volume, mode of application, emission sources,
degradation rates, etc.). Concentrations can be underestimated or overestimated
by models due to the complexity of the environments. Many processes are involved
in the dynamics of pollutants in the different environmental scenarios, which affects
directly to leaching and degradation processes. Thus, it appears that the exposure
models do not come up to the whole complexity of the real environment. Therefore,
although predicted concentrations cannot replace measurements, they suppose
a useful tool to choose target compounds which are important to be monitored
or to point out which compound form (metabolite or parent compound) and
compartments (liquid versus solid fraction) should be measured.
Ideally, measuring and modeling should be seen as complementary rather than
excluding approaches; the wisest recommendation would be making use of both
alternatives in order to benefit from their respective advantages. Unfortunately,
such desirable complementary approach is rarely seen together (see as instances
[9, 10]). In Table 1 are summarized the main strengths and weaknesses of both
procedures. The main drawback of measuring is that it is usually focused on certain
target analytes and there is thus low chance of finding new targets. Other aspects of
concern are their limited possibilities regarding time and space coverage (it is
impossible being everywhere at every time). As mentioned before, sampling
campaigns may be a limiting factor because of their prohibitive economic cost.
On other hand, the main advantage of experimental measurement is that it provides
reliable results that are quite independent of the laboratories (at least, it is true for
those that have an adequate Quality Assurance/Quality Control System). In turn,
modeling is fast and relatively affordable and has very good time and space
coverage possibilities, being, on the other hand, its main weakness the strong
dependence on the model chosen and its inherent uncertainty because of the lack
of reliable inputs.
30

Table 1 Comparative overview of strengths and weaknesses of analytical measurement vs. modeling in environmental studies (Adapted from [7, 11])
Analytical measurement Pros – Results obtained reflect well reality
– Repeatability and reproducibility of results (at least between good qualified labs)
– Measurements are independent of information/data sources
– Multipurpose analytical methods can cover many compounds on a single run
– Even the best model will ultimately need to be experimentally checked
– Discovery of new emerging contaminants is possible
Cons – Determination of compounds at very low quantities may be difficult
– Time and space coverage require expensive monitoring campaigns
– Sampling campaigns may miss crucial episodes
– Analytical measurements give a snapshot, rather than a continuous picture
– Expensive analytical equipment and method development
– Target monitoring may miss pollutants: “you only find what you are looking for”
Predicting (modeling) Pros – Very good coverage capabilities of time and space
– Computation equipment is affordable
– Possibility of application to hypothetical scenarios: “What if?”
– Useful for extrapolations to future (predictions on space and time, even for products not yet in the market)
– Simultaneous modeling of many compounds
– Once the model is set up are fast and cheap to use
Cons – Different models may render very different results
– Models are strongly dependent on parameter and data input
– Diffuse sources of pollution may be very difficult to model
D. Guillén et al.
Characterization of Environmental Exposure: Measuring Versus Modeling 31

3 New Trends in Analytical Chemistry for Measuring
Environmental Concentrations

As discussed in previous sections, measurements in the laboratory suppose the most
accurate solution for determining environmental concentrations. In this section the
main advantages of analytical measurements as well as the new trends in analytical
instrumentation and experimental methodologies are discussed.
Last decades, the trends of environmental analysis were focused on determining
organic “priority pollutants.” These priority pollutants are characterized by their
high toxicity, high environmental persistence, and/or high hydrophobicity. Some of
them cause endocrine disruption effects on aquatic organisms and consequently,
they could represent a risk to environment and human health. On reviewing
the literature, thousands of methodologies are presented for the determination of
these priority compounds including polychlorinated biphenyls (PCBs) [12, 13],
polyaromatic hydrocarbons (PAHs) [14], chlorinated pesticides [14], organotin
compounds [15], alkylphenolic compounds [16], polybrominated compounds
[17, 18], etc. Although there is a multitude of methods for their determination, still
today new analytical methodologies appear oriented towards improvements on their
determination by reducing the analysis time, the detection limits, sample manipula-
tion, etc. The development of multiresidue methods is also a current practice
in environmental monitoring, since it allows determining simultaneously a large
number of chemicals in a single analysis run.
In recent years the interest of environmental analytical chemistry was turned
to the so-called “emerging contaminants” or “new” unregulated contaminants
including pharmaceuticals, endocrine disruptors, detergents, personal care products,
plasticizers, flame retardants, gasoline additives, etc. These compounds are released
continuously to the environment and can be found in water, sediments, soils, etc. In
most of the cases they are found at trace level concentration (ng/L); therefore,
powerful analytical capabilities are required for their determination.
For this purpose, the gas (GC) and liquid chromatography (LC), coupled to mass
spectrometry (MS), are identified as the techniques par excellence. Whereas GC is
more addressed to the analysis of nonpolar and volatile compounds, LC is the
technique of choice for the separation of polar organic pollutants. MS has increas-
ingly become the preferred detector for the identification and quantification of
organic contaminants in environmental samples. MS offers some unique advantages
in terms of sensitivity and specificity. In the case of very complex matrices, such as
wastewater, sludge or biota, tandem mass spectrometry (MS/MS) offers a better
detection limit because of the reduction of “chemical noise” and thus an improve-
ment in the overall signal-to-noise ratio. In Table 2 are summarized some of the most
representative multiresidue analytical methods for monitoring classical and
emerging pollutants in environmental matrices are summarized.
With recent instrumental development, such as fast LC, fast GC and two-
dimensional gas chromatography (GCxGC) and advanced tandem hybrid MS
detection systems (i.e., QqTOF, QqLIT, Orbitrap) the analysis of complex mixtures
Table 2 Summary of some representative current analytical methods for quantitative determination of selected priority and emerging organic contaminants in
32

environmental samples. Adapted from [7]
Range of concentrations detected
Analytes Matrix Extraction method Detection in the environment REF
Pharmaceuticals River waters, effluent Online SPE LC-MS/MS River waters: [19]
Multi-residue of 74 wastewater and (QqLIT) < LOD-307 ng/L
compounds drinking water Effluent wastewaters:
<LOD-1,120 ng/L
Drinking water:
<LOD-201 ng/L
Pharmaceuticals River sediment Water: off-line SPE (Oasis HLB) LC-MS/MS River sediment: [20]
Multi-residue of 43 Particulate matter Solids: PLE (MeOH/H2O 1:2, v/v) and SPE (QqLIT) <LOD-222 ng/g
compounds River waters (Oasis HLB) Particulate matter:
<LOD-657 ng/g
River water:
<LOD-1,162 ng/L
Drugs of abuse Drinking water Off-line SPE (Oasis HLB) UPLC-MS/ Spanish tap water [21]
27 compounds MS Mean conc: <LOQ-50 ng/L
(QqQ) Median conc: <LOQ-24 ng/L
Tap water from other countries
Mean conc: <LOD-40 ng/L
Median conc: <LOD-37 ng/L
Drugs of abuse Influent and effluent On-line SPE LC-MS/MS Influent wastewater: [22]
17 compounds and wastewater and river (QqLIT) <LOD-3,790 ng/L
metabolites water Effluent wastewater: <LOD-
510 ng/L
River water: <LOD-346 ng/L
PFCs Sewage sludge PLE (MeOH) and SPE (Oasis WAX) LC-MS/MS Sewage sludge: <LOD- [23]
13 perfluorinated (QqLIT) 101 mg/Kg
acids, 4
perfluorosulfonates
and PFOSA
D. Guillén et al.
14 PFCs Surface, sea and sewage SPE (Oasis HLB) LC-TOF- Sea water: <LOD-4.2 ng/L [24]
water MS Harbor water: <LOD-12.8 ng/L
Surface water: <LOQ-38.9 ng/L
16 Pesticides River water Online SPE LC-MS/MS River water: <LOD-818 ng/L [25]
Triazines, phenylureas, (QqQ)
OPs,
chloroacetanilides,
thiocarbamates
28 priority pesticides River sediment UE (Hexane/Acetone, 1:1, v/v) GC-EI-MS River sediment: [26]
OCs, OPs, triazines, <LOD-450 mg/Kg
anilides
OPs pesticides and Sewage sludge UE (AcN 1% HAc) and DSPE (PSA) LC-MS/MS Sewage sludge: [27]
metabolites (QqQ) <LOD-344 ng/g
Nanomaterials Suspended material of UE (toluene) LC-MS/MS Wastewater effluent: [28]
C60 and C70 fullerenes wastewater effluents (QqLIT) <LOD-65,900 ng/L
9 UV-filters River, lake and treated SBSE TD-GC-MS Lake water: <LOD-250 ng/L [29]
wastewater River water: <LOD-30 ng/L
Treated wastewater:
<LOD-54 ng/L
8 UV filters Sewage sludge PLE (MeOH) UPLC-MS/ Sewage sludge: <LOD-9.17 mg/g [30]
MS
(QqQ)
11 PPCPs Surface and wastewaters SPE (Oasis HLB and Bond Elute Plexa) UPLC-MS/ Influent wastewater: [31]
4 preservatives, MS <LOD-5,613 ng/L
Characterization of Environmental Exposure: Measuring Versus Modeling

2 antimicrobials and (QqQ) Effluent wastewater:
5 UV filters <LOD-100 ng/L
Surfactants Wastewater and Water: SPE (C18) LC-MS Influent wastewater: [32]
LAS, CDEAs, NPEOs receiving coastal Sediments: PLE (Acetone-MeOH, 1:1) <LOD-1,920 mg/L
and DPs waters and Effluent wastewater:
sediments <LOD-872 mg/L
Sea water: <LOD-26 mg/L
(continued)
33
Table 2 (continued)
34

Range of concentrations detected
Analytes Matrix Extraction method Detection
in the environment REF
Marine sediments:
<LOD-86,940 mg/kg
Surfactants Soil amended with PLE (MeOH/H2O 90:10, v/v) and SPE (RP-C18) LC-MS/MS Soil amended with sludge: [33]
LAS and major sewage sludge (QqQ) <LOD-1,049 mg/kg
metabolites (SPC)
PBDEs, PCDDs, PCDFs Coastal sediments Soxhlet (toluene) and clean-up with silica gel GC-EI-MS Coastal sediments: [34]
and PCBs +alumina+PX-21 active carbon column <LOD-28,769 pg/g
19 Phytoestrogens, River water, one SPE (RP-18) LC-MS/MS Range of concentrations of [35]
progestogens and channel and a lagoon positive samples:
estrogens 0.34–366 ng/L
Estrogens and River sediment MAE (MeOH/H2O 25:75, v/v) and SPE (Oasis LC-MS/MS River sediment: <LOD-2.37 ng/g [36]
conjugates WAX) (IT)
PLE pressurized liquid extraction, SPE solid phase extraction, UE ultrasonic extraction, DSPE dispersive solid phase extraction, SBSE stir bar sorptive
extraction, TD-GC-MS thermal desorption-gas chromatography-mass spectrometry, LAS linear alkylbenzene sulfonates, CDEAs coconut diethanol amides,
NPEOs nonylphenol ethoxylates, DP degradation products, SPC sulphenyl carboxylates, PCDD dibenzo-p-dioxins (PCDD), PCDF dibenzofurans, PCBs
biphenyls
D. Guillén et al.
Characterization of Environmental Exposure: Measuring Versus Modeling 35

in environmental matrices has been considerably improved. Ultra high performance
liquid chromatography (UPLC) has recently arisen as a technique that uses short
columns, with narrow bore columns, high mobile phase flow-rates and ultra-high
pressures. Although UPLC relies on the same selectivity and retention principles
than HPLC, their smaller stationary-phase particle diameter (sub-2 mm) allows
shortening analysis time up to nine times comparing to the conventional HPLC.
Therefore, UPLC allows working with high mobile phase flow rates and ultrahigh
pressures which allows developing faster methods with improved chromatographic
separations. Shortening the analysis time is important for attaining the high sample
throughput often required in laboratories conducting monitoring studies.
The recently developed technique known as “two-dimensional gas chromatogra-
phy (GCxGC)” is gaining significant popularity for complex sample analysis. GCxGC
separation is attained by coupling two GC columns with different selectivity (usually
the first is a nonpolar column and the second a polar stationary phase) allowing to
separate compounds first by their volatility and then for their polarity. The advantages
of this recent technology are increased sensitivity and greater utilization of separation
space, which helps reduce the problem of co-elution in complex samples. GCxGC is
often coupled with a time-of-flight (ToF) detector because of its rapid acquisition
capability [37].
Regarding sampling and sample preparation, solid phase extraction (SPE) still
remains as the most widely used mean of extraction and concentration of organic
contaminants in aqueous matrices. A new SPE device called “Bag” extraction
consisting of a polystyrenedivinylbenzene enclosed in a woven polyester fabric,
which can be immersed in water samples, has been reported during the last 2 years.
For instance, measured concentrations of pharmaceuticals using this approach have
been shown to be comparable to those obtained with Oasis HLB cartridges, which is
one of the most widely used polymers in SPE extraction [37]. The benefits of using
this Bag SPE technique are the use of handling, unattended water extraction, and
that no further filtration is needed.
Other recent approaches for the analysis of organic contaminants in water
samples involve: (1) automation through coupling of sample preparation units
and detection systems (i.e., online solid phase extraction (SPE)-LC, online solid
phase micro extraction (SPME)-LC or (SPME)-GC), (2) application of tailored
sorbents (i.e., molecular imprinted polymers, immunosorbents, nanomaterials),
and (3) integration of several sample preparation steps into one (i.e., application
of passive samplers for simultaneous sampling, extraction and enrichment of
pollutants from liquid and gaseous samples, such as the “polar organic chemical
integrative samplers” (POCIS)). POCIS devices have the capacity to handle large
volumes of water over long periods, thereby giving time-weighted average (TWA)
concentrations and allowing monitoring episodic changes in environmental con-
taminant concentrations, which are often misinterpreted with conventional discrete
samples [38].
For solid samples PLE, microwave-assisted extraction (MAE) and supercritical
fluid extraction (SFE) [39, 40] are the preferred extraction methods.
36 D. Guillén et al.

Current analytical methods only focus their attention on parent target compounds
and rarely include metabolites and transformation products, which sometimes can be
more toxic and persistent than original compounds. Moreover, identification of
reaction pathways and identification of transformation products are of crucial
importance in understanding the fate or organic contaminants in the environment.
On the other hand, high complexity of environmental samples sometimes requires
application of high-resolving power techniques in order to provide additional
structure information needed for unequivocal identification of contaminants
and confirmation of positive findings. The introduction of Orbitrap, TOF, QqTOF
and QqLIT instruments, which allow the simultaneous determination of both
parent and transformation products, within a single analytical run, overcomes this
drawbacks and provides a higher degree of certainty in compound identification. In
comparison with triple quadrupole mass spectrometers, which operate at unit reso-
lution and generally in the selected reaction monitoring (SRM) or multiple reaction
monitoring mode (MRM) modes for specific target analytes, TOF, QqTOF, and
orbitrap mass spectrometers are capable of acquiring full-scan mass spectra at high
resolution for all analytes without loss in sensitivity. Since these instruments have
high resolution (at least 10,000 and higher) at full-width-half-maximum (fwhm)
peak height, isotopic patterns are evident and chemical structures can be proposed
for unknowns or confirmed for target analytes [37, 41]. Concerning Orbitrap
instruments, they still do not have such a widespread use due to higher costs.
Nevertheless, the Orbitrap technology introduced by Thermo Fischer Scientific
(San Jose, CA, USA) seems to be one of the future mass spectrometry trends due
to high-resolving power of the Orbitrap [41]. Regarding QqLIT, it allows
performing sensitive quantitative analysis combined with unequivocal identification
due to the application of the Information Dependent Acquisition (IDA) function,
where a targeted screening is performed in combination with an Enhanced Product
Ion Scan, achieving MS/MS spectra that are matched with MS/MS spectra present in
a library [41].
Due to scientific and public concern about environmental pollution, new
developments in environmental analysis are focused on the implementation of
environmental-friendly practices in the laboratories. Main strategies are addressed
to saving energy and to reduce solvent consumption with the minimum sample
manipulation by using on-site, online, and direct analysis (e.g., biosensors) [42].

4 Predicting Environmental Concentrations Through Modeling

Owing to the complexity and dynamic character of real environmental scenarios, it
is not always possible to predict concentrations with desirable level of precision.
Nevertheless, even though experimental measurements are not replaceable by
PECs, this approach can still serve as a useful tool for supporting hazard assessment
programs. Making predictions also can help identifying compounds or compounds
families that should be monitored, as well as what the most exposed compartments
Characterization of Environmental Exposure: Measuring Versus Modeling 37

are. In order to carry out a realistic prediction of concentrations, several questions
must be first answered: What is the purpose of the predictions? What decisions will
be made after the approach? What precision is required? Which are the weaknesses
of the approach? The prediction will be successful only if it satisfies the initial
requirements. Otherwise experimental measurements will be necessary.
For environmental purposes, different approaches for predicting environmental
concentrations have been used. Table 3 gives some representative examples of
these studies. The input data required are usually the production or consumption of
chemicals in the studied area that allow estimating their emission rates to the
environment. Depending on the complexity of the scenario, different number of
variables can be used to achieve the prediction.
Mueler et al. and Gottschalk et al. [43, 44] presented a model for predicting
concentrations of nanoparticles including nano-Ag, nano-TiO2, nano-ZnO,
fullerenes, and carbon nanotubes (CNT) in different environmental compartments.
The results of this study demonstrated that modeling is a meaningful utility to carry
out quantitative risk assessment of nanoparticles.
Stuer et al. [46] evaluated the presence of the 25 most used pharmaceuticals in
the primary health sector in Denmark (e.g., paracetamol, acetyl salicylic acid,
diazepam, and ibuprofen). They compared PECs with experimental determinations
and they conclude that measured concentrations were in general within a factor of
2–5 of PECs. Carballa et al. [45] also determined PECs for pharmaceuticals (17),
musk fragrances (2) and hormones (2) in sewage sludge matrix. For that purpose
they used three different approaches: (1) extrapolation of the per capita use in
Europe to the number of Spanish inhabitants for musk fragrances; (2) annual
prescription items multiplied by the average daily dose for pharmaceuticals and;
(3) excretion rates of different groups of population for hormones. They indicated
that these PECs fitted with the measured values for half of them (carbamazepine,
diazepam, ibuprofen, naproxen, diclofenac, sulfamethoxazole, roxithromycin,
erythromycin, and 17a-ethinylestradiol).
PECs also were calculated by Domènech et al. [47] for determining the presence
of cocaine and its main metabolite (benzoilecgonine) in different environmental
compartments (air, water, soil, etc.).
Additionally, the integration of geographic information system (GIS) with
analytical data is an effective procedure in addressing the problem of spatial and
temporal variability of the different parameters involved in the environmental fate
of chemicals. Based on accurate local estimations, GIS-based models would then
also allow deriving realistic and representative spatially averaged regional PECs.
Table 4 shows some studies that have used GIS-based methodologies to perform a
site-specific risk assessment of PECs in different exposed ecosystems.
Verro et al. [53] evaluated the risk associated with the presence of alachlor
herbicide in surface waters (released by drift and runoff) from Lombardia region
(Northern Italy). They applied a GIS-based model for representing the obtained
PECs in risk maps showing a static image of a worst-case simulation in each river
subbasin.
38

Table 3 Review of some relevant studies addressed to the estimation of PECs. Main inputs used for determining PECs are also indicated
Compounds Matrix Studied location Model inputs Ref.
Nano silver (nano-Ag), Air, soil and water Switzerland – Estimated worldwide production volume [43]
nano TiO2 (nano-TiO2) – Allocation of the production volume to product
and carbon nanotubes categories
(CNT) – Particle release from products
– Flow coefficients within the environmental
compartments
Nano-TiO2, nano-ZnO, Air, surface water, STP effluent, U.S., Europe and – Annual production, manufacturing, and [44]
nano-Ag, carbon and sewage sludge, soil, Switzerland consumption
nanotubes (CNT) and sludge-treated soil and – Waste treatment processes (sewage treatment, waste
fullerenes sediment incineration, landfill and recycling)
– Deposition and elimination/degradation of
engineered nanomaterials
17 PhACs, 2 musk Raw sewage Galicia and Cataluña – Per capita annual consumption [45]
fragrances and two (Spain) – Number of inhabitants served by each STP
hormones – Average flow treated
25 PhACs Water Denmark – Amount of PhACs used by year (kg/year) [46]
– The removal in percent
– Number of habitants in Denmark
– Volume of waste water per day per capita
– Dilution factor in the environment
Cocaine and its metabolite Air, water, soil, sediments and Regional environmental – Initial cocaine intake [47]
benzoilecgonine (BE) suspended matter system – Partial degradation of the parent compound to BE
– Treatment of wastewater
– Environmental fate
CNT carbon nanotubes, PhACs pharmaceuticals, BE benzoilecgonine
D. Guillén et al.
Table 4 Some representative studies which determine chemical concentrations in the environment using models based on GIS methodology
Environmental
Chemicals Application area matrix Model inputs REF
(Heavy metal) Zinc Lebano Soil – Soil pH [48]
– Organic matter content
– Lithology
– Surroundings of waste areas
– Proximity to roads
– Distance to drainage line
– Slope length
(Consumer-product ingredients) Boron, River Itter (Germany) Surface water – Consumption figures in consumer products [49]
LAS, EDTA, NTA and triclosan – WWTP-elimination
– Sewer removal
– In-stream-removal
– Background concentration
(Pharmaceuticals) Ethinyl oestradiol, Aire river (UK), Lambro Surface water – Product consumption [50]
paracetamol, aspirin, river (Italy) and Rur river – Worst-case influent
dextropropoxyphene, clofibrate and (Germany) – Excreted post-metabolism
oxytetracycline – WWTP removal
– River water die-away
(Pesticide) Triclosan Aire River (UK) Surface water – Physical, chemical, and biochemical [51]
parameters
– Geographical production and consumption
patterns
Characterization of Environmental Exposure: Measuring Versus Modeling

(Pesticide) Pyrethroids European continent Soil and water – Total pesticide use [52]
– Spatial distribution of crops
– Crop types (cereal, maize, oilseeds, citrus, etc.)
– Runoff and soil moisture
– Fate and transport parameters
(continued)
39
Table 4 (continued)
40

Environmental
Chemicals Application area matrix Model inputs REF
(Pesticide) Alachlor Lombardia Region (Northern Surface water – Meteorological data [53]
Italy) – Application rate
– Active ingredient lost by drift
– Percentage of active ingredient lost by runoff
(Cyclic volatile methyl siloxane) D5 Nene and Great Ouse Rivers Surface water – Influent dry weather flow [54]
(England) – WWTP influent concentration
– Effluent discharges flow
LAS linear alkylbenzolsulfonate, EDTA ethylenediamine-tetraacetic-acid, NTA nitrilotriacetate, D5 decamethylcyclopentasiloxane
D. Guillén et al.
Characterization of Environmental Exposure: Measuring Versus Modeling 41

Matrix Environmental processes Climate conditions
Properties - Sorption/desorption, Temperature, humidity, wind
speed, solar radiation, rainfall. Biological and
- Volatilization,
- pH, non-biological
- TOC, - Precipitation, degradation
- Soil texture, Hydrologic conditions processes
- Dissolution Water flow, water column depth,
- Porosity,
- Bulk density - Leaching turbidity, etc.

Air Soil Water Biota Sediment

TOC: Total organic carbon

Fig. 2 Main processes and factors affecting the fate and transport of chemicals in the
environment

Regardless the complexity of the models used for predicting environmental
concentrations, they share some common requirements regarding to the influencing
factors that govern the occurrence and fate of chemicals in the environment:
(1) anthropogenic factors (emission rates, types of emissions and sources, waste
management, etc.); (2) intrinsic physical–chemical properties of the chemical
compounds and (3) environmental (external) conditions. In Fig. 2 are represented
some of the key factors that influence the fate and behavior of chemicals.
The first step for the determination of PECs is the recognition of the anthropogenic
activities that constitute the main sources of chemicals into the environment. Exposure
models are based on estimations through exposure-related databases, manufacturing
and trade inventories, sales reports, previous experimental studies and surveys.
Chemicals present in products can be released into the environment in any stage of
their life cycle (during their production, the finished product or waste). Therefore
estimating emissions from finished products sometimes may be even more difficult
because the composition and amount of chemicals present in these products is often
lacking. The mode of use (closed cycle, spreading or used as chemical additives) and
emission characteristics (point or diffuse) are also some of the factors to be considered.
Once chemicals are released into the environment, their behavior and fate are
highly dependent on their physicochemical properties. These intrinsic properties of
chemicals are decisive for their mobility throughout the different environmental
compartments. Some of the most representative properties involved in mobility and
behavior of chemicals are: partition constants (KOW and KOC), Henry’s law constant,
vapor pressure, solubility, evaporation temperature, as well as processes related to
degradations (biological and nonbiological) such as hydrolysis, adsorption/desorp-
tion, and photolysis. Sorption/desorption processes play a major role in the availability
of chemicals reaching target living organisms and the amounts that can be volatilized,
leached, and/or degraded [55]. There are evidences that the mobility of chemicals in
soils depends on several factors including the soil geologic characteristics (presence of
42 D. Guillén et al.

gravel, clay, sand, etc.), particle size, porosity, pH, conductivity, the total organic
carbon and the dissolved organic carbon fraction in water [56].
Finally, the third major input information required is external (i.e., extrinsic to the
compound itself): the environmental physical conditions (see Fig. 2). Temperature
and water regimes are often the most determinant factors which affect the mobility
of chemicals in the environment by accelerating volatilization or sorption processes.
Solar radiation is also crucial in the chemicals fate since it is strongly related to
photodegradation and volatilization processes as well.
Therefore any attempt to model the spatial occurrence and fate of chemicals in
the environment will require an appropriate choice of all the factors discussed
above, which have a definite influence on the behavior of the chemicals considered.
Figure 2 summarizes some of the most relevant. It is worth mentioning that the
availability of spatial data sets has been greatly enhanced by the current progress
achieved on remote sensing technologies [57, 58].

5 Future Challenges

Though it is impossible to anticipate all the directions in which environmental risk
assessment will expand during the forthcoming years, below are presented some hot
issues that nowadays are already attracting considerable scientific research.
Sometimes for some very potent pollutants analytical methodologies provide
limits of detection (LODs) higher than the concentrations that cause effects, as
derived from ecotoxicological studies. Therefore efforts in the field of analytical
chemistry (see Sect. 2) are focused on making available the necessary analytical
capabilities to detect pollutants at the required low levels found in the environment.
This was the case of pharmaceuticals, illicit drugs, perfluorinated compounds
(PFCs), sunscreens/UV filters, etc. few years ago. However, this list is likely to
increase with new family candidates.
During recent years several groups of organic contaminants have emerged,
including sucralose (and other artificial sweeteners), nanomaterials, disinfection
by-products (DBPs), siloxanes, and algal toxins among others. Moreover, there is
a further emerging group of contaminants of concern, the ionic liquids, whose
occurrence and analysis in the environment points are the hottest topic within
environmental analytical chemistry. Ionic liquids are salts with a low melting
point (<100 C) that are being promoted as “green chemistry” replacements to
traditional solvents used in industry because they have low volatility and flamma-
bility. In fact, their use is highlighted in many papers as an innovative approach to
sustainable chemistry. However, there is still limited information about their toxicity
and environmental fate [37, 59].
The occurrence, behavior, and toxicity of all these emerging contaminants
continue to be an intensive area of research, especially investigations about their
removal from environmental waters (e.g., through advanced oxidation, photolysis,
microbial degradation, etc.). Therefore, the identification of intermediates and
degradation products originated as a result of these removal mechanisms is of
Characterization of Environmental Exposure: Measuring Versus Modeling 43

crucial importance, as well as the evaluation of their toxicity, or the biological
activity for the transformation products. Although many researchers are combining
analytical chemistry with the study of biological effects, the identification and
structural elucidation of transformation products of organic contaminants still
require further analytical efforts.

6 Conclusions

As it has been shown in this chapter knowing the concentrations of chemicals in the
environment is a key aspect in order to carry out meaningful hazard and risk
assessment studies. Predicting concentrations of chemicals can serve as a quick
and robust way to produce an acceptable screening level assessment; however if
further precision is desired, the complexity of real environmental scenarios can
make it a cumbersome and unaffordable task. Models improvement requires not
only refining their computation algorithms but also and more important,
implementing new inputs and processes in order to better describe real scenarios.
Laboratory measurements are still the most reliable way for determining envi-
ronmental concentrations of chemicals (organic and inorganic) but this procedure
supposes a great investment of time and money on both analytical equipment and
monitoring efforts. Even so, monitoring has some obvious and unavoidable limits in
terms of space and time coverage. The use of sensors and remote sensing techniques
working on line at real time can only partially overcome such difficulties, but still
the great majority of micropollutants of concern cannot be surveyed using these
techniques.
In the Environmental Chemistry domain there is a growing need to develop
reliable analytical methods, which enable a rapid, sensitive, and selective determi-
nation of pollutants in samples, at trace levels concentrations. Multi-residue analyt-
ical methodologies are becoming more utilized for routine analysis since they enable
obtaining on a single run a wider and reliable knowledge about the occurrence of
groups of compounds with similar properties (e.g., pharmaceuticals, illicit drugs,
pesticides, and semivolatile compounds).
To conclude, a combination of both modeling and measuring procedures should
be the most appropriate and wise recommendation for assessing chemical exposure
in environmental scenarios.

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Environmental Fate Models

N. Suciu, T. Tanaka, M. Trevisan, M. Schuhmacher, M. Nadal, J. Rovira,
X. Segui, J. Casal, R.M. Darbra, and E. Capri

Abstract The environmental fate of chemicals describes the processes by which
chemicals move and are transformed into the environment. Environmental fate
processes that should be addressed include: persistence in air, water and soil;
reactivity and degradation; migration in groundwater; removal from effluents by
standard wastewater treatment methods and bioaccumulation in aquatic or terres-
trial organisms. Environmental fate models are by no means compulsory for
managing priority substances. Efficient source control can be done without them,
i.e. by reducing emissions gradually and monitoring the environment to track
changes. However the environmental fate models are proposed for use for two
main reasons: (a) because the quantitative models can improve the understanding of
the managed system and (b) because the models can be used to predict long-term
impacts of planned actions. Furthermore the residence times of some of the priority
substances may be very long (e.g. 50 years for mercury in water column); therefore,
only monitoring could be not enough to detect if the taken measures are enough to
reach the good ecological status. The use of environmental fate models in decision
making is not a new concept. They are routinely used in the framework of

N. Suciu (*), M. Trevisan, and E. Capri
Institute of Agricultural and Environmental Chemistry, Università Cattolica del Sacro Cuore,
Via Emilia Parmense 84, 29122 Piacenza, Italy
e-mail: nicoleta.suciu@unicatt.it
T. Tanaka
INERIS, Institut National de l’Environnement Industriel et des Risques, Parc Technologique
Alata, BP 2, 60550 Verneuil-en-Halatte, France
M. Schuhmacher, M. Nadal, and J. Rovira
School of Chemical Engineering, Universitat Rovira i Virgili, Av. Paı̈sos Catalans 26,
43007 Tarragona, Spain
X. Segui, J. Casal, and R.M. Darbra
Department of Chemical Engineering, Universitat Politècnica de Catalunya, Diagonal 647,
08028 Barcelona, Spain

B. Bilitewski et al. (eds.), Global Risk-Based Management of Chemical Additives II: 47
Risk-Based Assessment and Management Strategies, Hdb Env Chem (2013) 23: 47–72,
DOI 10.1007/698_2012_177, # Springer-Verlag Berlin Heidelberg 2012,
Published online: 24 July 2012
48 N. Suciu et al.

environmental risk assessment. The output of environmental fate models can be
expressed as time series of predicted concentrations in different medium of both
indoor and outdoor environments.

Keywords Chemicals, Fate, Modelling, Risk assessment

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2 Multimedia Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.1 Fugacity and Markov Chain Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3 Models Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.1 Qwasi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.2 ChemCAN Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
3.3 CHEMGL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
3.4 GREAT-ER Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
3.5 SimpleBox Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
3.6 BETR Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.7 CalTOX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.8 XtraFOD Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.9 2-FUN Tool . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67

1 Introduction

The environmental fate of chemicals describes the processes by which chemicals
move and are transformed into the environment. Environmental fate processes that
should be addressed include: persistence in air, water and soil; reactivity and
degradation; migration in groundwater; removal from effluents by standard waste-
water treatment methods and bioaccumulation in aquatic or terrestrial organisms.
To address media-specific problems, single-media models for air, surface water,
groundwater and soil pollution have been developed and used by different
disciplines. Although these models generally provide detailed description of the
pollutant distribution in space and time and incorporate mass transfer from other
media as boundary conditions, they are not capable of characterizing the total
environmental impact of a pollutant release. Multimedia models have been, there-
fore, developed to predict the concentration of chemicals in multiple environmental
media simultaneously with consideration of chemical transport and transformation
within and among media [1].
In this chapter, a brief description of the concepts and tools available for
multimedia modelling to support the environmental risk assessment is given. The
environmental fate assessment is the base of a more complex study, the
Environmental Fate Models 49

Fig. 1 Integrated environmental health risk assessment scheme (based on [2]); the boxes within
the red line are the issues discussed in this chapter

environmental health and risk assessment (Fig. 1). Each of the tools is summarized
and evaluated by a fixed number of principal characteristics:
– Impact categories (model outputs): eco-toxicity impacts and/or human toxicity
impact
– Exposure routes: ingestion, inhalation, dermal
– Fate, exposure and effect: if fate, exposure and effect analyses are included or
not
– Chemicals considered: organic pollutants and/or metals
– Media considered: air, water (fresh, ground, sea, etc.), soil, sediment, vegetation,
food chain, etc.
– Spatial variation: regional scale, continental scale, global scale, country and
seas boundaries
– Source code availability
– Model availability: pay model or free model
– Availability for sensitivity and uncertainty analyses
– Population category: if the differences in man/woman and adult/child are
considered or not
This chapter considers the recently developed tools and the latest versions of the
old tools. Some of the tools comprise not only the environmental compartments
used on environmental risk assessment but also the human compartment necessary
for human health risk assessment. For this reason, when summarizing the models,
as described in the second part of this chapter, several characteristics of human
compartment are discussed as well. However, a detailed description of human
compartment together with a wide range of tools developed for exposure and
human risk assessment is presented in the next chapter.
50 N. Suciu et al.

2 Multimedia Models

Based on the descriptions of spatial variation in each environmental compartment,
multimedia models can be categorized into multimedia compartmental models
(MCMs) [3–20], spatial multimedia models (SMs) [21–24] and spatial multimedia
compartmental models (SMCMs) [25–27]. MCMs assume homogeneous landscape
properties in each medium and assume all environmental compartments are well
mixed. SMs are collections of single-media models in which the output of one
model serves as the input to the others. Each individual model in the SMs is a spatial
model describing the variation of environmental properties in one or more
directions. SMCMs are similar to MCMs, but consider one or more environmental
compartments as nonuniform regions.
In order to achieve that an environmental fate model is successfully applied in a
screening level risk assessment and ultimately incorporated into the decision-
making tools, the model should have computational efficiency and modest data
input. Moreover, the model should incorporate all relevant compartments and all
sources of contamination and should consider the most important mechanisms of
fate and transport. Although spatial models describe the environment more accu-
rately, such models are difficult to apply because they require a large amount of
input data (e.g., detailed terrain parameters, meteorological data, turbulence
characteristics and other related parameters). Therefore, MCMs are more practical,
especially for long-term environmental impact evaluation, because of their modest
data requirements and relatively simple yet comprehensive model structure. In
addition, MCMs are also widely used for the comparative risk assessment of new
and existing chemicals [28–33].
Among MCMs reported in environmental science literature, the following
models are most widely used: CalTOX [7, 8], ChemCAN [12], HAZCHEM [10],
SimpleBox [9], Qwasi [34], and 2-FUN TOOL [20]. Most of these models consider
the lower atmosphere (troposphere), surface water, soil and sediment as the main
compartments, with some sub-compartments or add-on indirect exposure models
(e.g., vegetation) included. CalTOX has the capability to estimate chemical con-
centration in groundwater based on the leachate from the vadose-zone soil, and
ChemCAN considers the chemical transfer from the air compartment to higher
altitude. However, all of these models do not treat some important compartments,
such as the stratosphere and groundwater, as separate compartments. The inclusion
of the stratosphere compartment in a model enables an individual to estimate the
ozone depletion potential for existing or new chemicals.
Although some of the other existing models treat the vegetation as a separate
compartment [14, 35, 36] and some include the groundwater as a main compart-
ment [4, 11], none of the models incorporates all important compartments at the
same time. However, ignoring some important compartments may result in large
difference of concentration in the media of interest. For example, the inclusion of a
canopy compartment decreases the average air concentrations during the growing
season by a factor of 5 for some semi-volatile organic compounds [37]. Therefore,
Environmental Fate Models 51

the CHEMGL multimedia model has been developed by Zhang et al. [38], which
includes all the relevant aforementioned compartments. This may represent an
improvement over the existing models developed before.

2.1 Fugacity and Markov Chain Principles

Most of the above-mentioned models are based on the fugacity principle. The term
“fugacity” was introduced in 1901 by G.N. Lewis to describe the “escaping”
tendency of a chemical species from a particular environmental compartment
(e.g., air, water, soil, etc.). Where chemical potential within a particular compart-
ment is related logarithmically to concentration, the equilibrium criterion of fugacity
is linearly related to concentration. Fugacity (f) has units of pressure and environ-
mental compartments, in equilibrium with each other, have equal fugacity values
(i.e., the tendency to leave one compartment and enter a second is equal to the
tendency of the chemical to leave the second and enter the first). Each environmental
medium has a certain fugacity capacity (Z) that describes the relationship between
chemical concentration and fugacity in the same way that heat capacity describes the
change in temperature of a given material for a particular input of heat. Thus,
environmental media with high Z values can retain greater amounts of a given
chemical while maintaining low fugacity values.
The earliest or Level I fugacity models simulate the simple situation in which a
chemical achieves equilibrium between a number of phases of different composi-
tion and volume. The prevailing fugacity is simply f ¼ M/∑Vi  Zi, where M is the
total quantity of chemical (mol), Vi is volume (m3), and Zi is the corresponding
phase Z value (mol Pa1 m3). Although very elementary and naive, this simulation
is useful as a first indication of where a chemical is likely to partition. It is widely
used as a first step in chemical fate assessments.
More realistic Level II fugacity models introduce the rate of chemical reaction or
degradation and advection, but interphase equilibrium is still assumed. Level III
fugacity models introduce inter compartmental transfer rates, thus equilibrium no
longer applies. For Level III fugacity models it is then necessary to specify the
chemical’s mode-of-entry to the environment, that is, to air, water, or soil, or some
combination of these media. Valuable insights obtained from these models include
those of overall chemical persistence or residence time and potential for long-range
transport (LRT) in air or water. Level IV fugacity models, which involve the
solution of differential mass balance equations, can be used to describe the time
dependent or dynamic behavior of chemicals.
Besides the fugacity models, the environmental science literature reports the use
of models based on Markov chain principle to evaluate the environmental fate of
chemicals in multimedia environment. Markov chain is a random process, and its
theory lies in using transition matrix to describe the transition of a substance among
different states [39, 40]. If the substance has all together n different kinds of states,
52 N. Suciu et al.

which are expressed as i ¼ 1, 2, . . ., n, the transition matrix would be described as
the following matrix:
0 1
p11 p12  p1n
B p21 p22  p2n C
P¼B
@ 
C;
   A
pn1 pn2  pnn

where the element pij in the matrix is the transition probability for the substance
transiting from state i to j in each unit time. Supposing the initial state vector of the
substance is T(0) ¼ (y10, y20, . . ., yn0), at k time, the state vector will be

TðkÞ ¼ Tð0Þ  Pk:

This approach has been extensively applied to fields as agriculture [41, 42],
forestry [43], biology [44, 45], medicine [46, 47], business [48, 49] and chemical
engineering [50, 51], whereas in environmental protection, it was used to evaluate the
operation of environmental facilities [52], and the transportation of pollutants along
the food chain in ecological system [53]. However, Markov chain approach used for
evaluation of environmental fate of chemicals in environment multimedia was
recently adopted as reported by Zhang and Dai [54] and Dazhi and Xuqian [55].
The studies were developed at regional scale and mainly for PAHs organic pollutants.

3 Models Description

As already mentioned before, a list of nine models, comprising six models describ-
ing the fate and transport of chemicals in the environmental compartments (Qwasi,
ChemCAN, CHEMGL, GREAT-ER, SimpleBox, BETR) and three models able to
assess the fate and transport of chemicals in the environmental and human
compartments (CalTOX, ExtraFod, 2-FUN Tool) are described in this section.
The next chapter gives detailed descriptions of the human compartment and the
processes necessary for exposure and human health risk assessment.

3.1 Qwasi

The quantitative water air sediment interaction (Qwasi) model was developed in
1983 in order to perform a mathematical model which describes the behavior of
the contaminants in the water. Since there are many situations in which chemi-
cal substances (such as PCBs, pesticides, mercury, etc.) are discharged into a
river or a lake resulting in contamination of water, sediment and biota, it is
interesting to implement a model to assess the fate of these substances in the
aquatic compartment [34].
The Qwasi model estimate the fate of a chemical in a water system (lake, river,
etc.) consisting of water, bottom and suspended sediments, and air. The model is
Environmental Fate Models 53

(BOTH RAIN & AIR PARTICLES
IN EQUILIBRIUM WITH AIR)
fA Pa
AIR AIR PARTICLE
AIR /WATER EXCHANGE
fI Pa RAIN-OUT DEPOSITION
(WET & DRY) ABSORPTION VOLATILIZATION

AIR
GM,DM GQ,DQ DV DV
AW m2
WATER WATER
INFLOW GI,DI GJ,DJ OUTFLOW
GX,DX WATER GY,DY SUSPENDED
FISH & SUSPENDED SEDIMENT SEDIMENT
SUSPENDED IN EQUILIBRIUM WITH WATER OUTFLOW
SEDIMENT
INFLOW VW m3 DW WATER
TRANSFORMATION
fW Pa
3 3
EMISSIONS E VB m VP m

SEDIMENT SEDIMENT SEDIMENT/WATER
RESUSPENSION DEPOSITION DIFFUSION
AS m2
GR,DR GD,DD DT DT

SEDIMENT DS SEDIMENT
TRANSFORMATION
GB,DB
VS m3 fs Pa
SEDIMENT
BURIAL

Fig. 2 Qwasi processes considered [34]

Table 1 Principal characteristics of Qwasi model (based on [34])
Principal characteristics Mathematic for fate calculations of water systems
Impact categories Ecotoxicological effects
Exposure routes Not considered
Fate, exposure and effect Only fate of chemicals in water systems
considered
Chemical considered Organic and inorganic chemicals
Media considered Not considered
Spatial variation Local scale
Source code availability Yes, equations available
Model availability Yes
Dynamic or steady-state Both steady an unsteady state considered
Availability for sensitivity and uncertainty Not considered
analyses
Population category Not considered

based on the fugacity concept which provides an overview of the contaminants in
the aforementioned compartments.
The model is composed by different equations which in all cases can be used in
unsubscribed format in a basic language program. An important point to highlight is
that Qwasi takes into account both steady and unsteady state solutions for the
equations for systems involving contamination of lakes (or rivers). The equations
considered by Qwasi involve more than 15 physicochemical processes (such as
partitioning, sediment transport, deposition, etc.) to estimate the fate of the studied
system. These processes and the main involved variables and parameters are
summarized in Fig. 2.
As summary, the principal characteristics of the Qwasi model are listed in
Table 1.
54 N. Suciu et al.

3.2 ChemCAN Model

The ChemCAN model describes the fate of a chemical in a region, assuming steady
state conditions in the environment. The model estimates average concentrations in
four primary environmental media consisting of air, surface water, soil, and bottom
sediment, and three secondary media consisting of groundwater, coastal water and
terrestrial plants. Chemical fate is determined through the solution of the set of
mass balance equations for the primary media as described by Mackay [56]. The
model is intended to assist in human exposure assessment where a specific target
population may be identified.
This model was originally designed for use in Canada. Therefore, a database
of 24 regions of Canada is available. However, other regions can be defined by
the user. In the model, the appropriate dimension of surface areas is set between
100 km  100 km and 1,000 km  1,000 km. The regional divisions of Canada
were based on the eco-zones identified by Environment Canada and with consid-
eration of the distribution of population and industrial activity, political
boundaries, drainage basins, and climate to give areas of sufficiently homoge-
neous ecological conditions such that meaningful assessments of chemical fate
can be conducted.
The transparency of this model was achieved by making it possible for the user to
view the equations within the model. By viewing a section of the program code, the
user can know how this steady-state model mimics the physical reality. The model
is intended to provide regionally specific estimates of chemical concentrations in
the primary media. These estimates can be compared to monitoring data and be
used for exposure estimation.
A current application of this model was presented in Webster et al. [57] and its
main characteristics are presented in Table 2.

Table 2 Principal characteristics of the ChemCAN model
Principal characteristics Multimedia model with steady-state condition
Impact categories Human toxicity
Exposure routes Not specified
Fate, exposure and effect Fate
Chemical considered Organic compounds and non-volatile compounds
Media considered Air, surface water, soil, bottom sediment, groundwater,
coastal water, and terrestrial plants
Spatial variation Regional
Source code availability Yes
Model availability Yes
Dynamic or steady-state Steady-state
Availability for sensitivity and No
uncertainty analyses
Population category No
Environmental Fate Models 55

3.3 CHEMGL

Increasing concern about environmental problems as ozone depletion, groundwa-
ter pollution and human health risks via exposure from the food web suggests it
would be valuable to construct a model that includes the compartments of the
upper atmosphere (stratosphere), groundwater and vegetation. The CHEMGL
model was developed with this scope. Furthermore, the model is capable of
providing the information about whether a chemical will accumulate in the
lower atmosphere or upper atmosphere. If a chemical accumulates in the air
boundary layer (ABL), it will cause problems locally. However, if it accumulates
in the stratosphere, it presents a great possibility to lead to global problems.
Moreover, most environmental multimedia models are used for exposure assess-
ment, but few are linked with decision-making tools for screening level manufacturing
process design. CHEMGL has the advantage of a possible incorporation into an
economic and environmental decision analysis tools. This tool allows an individual
to make decisions for manufacturing processes based on environmental, safety and
economic criteria. In such tools, CHEMGL is used to estimate the concentration of a
chemical and is linked with a risk index calculator for the evaluation of several
environmental impacts resulting from chemical manufacturing [58].
As shown in Fig. 3, CHEMGL considers 10 major well-mixed compartments: air
boundary layer, free troposphere, stratosphere, surface water, surface soil, vadose
soil, sediment, ground water zone, plant foliage and plant route. In each compart-
ment, several phases are included, for example, air, water and solids (organic
matter, mineral matter). A volume fraction is used to express the ratio of the
phase volume to the bulk compartment volume. Furthermore, each compartment
is assumed to be a completely mixed box, which means all environmental
properties and the chemical concentrations are uniform in a compartment. In
addition, the environmental properties are assumed to not change with time.
Other assumptions made in the model include: continuous emissions to the
compartments, equilibrium between different phases within each compartment
and first-order irreversible loss rate within each compartment [38].
The main characteristics of the CHEMGL model are summarised in Table 3.

3.4 GREAT-ER Model

The GREAT-ER model was developed as an aquatic chemical exposure prediction
tool for use within environmental risk assessment (ERA) schemes and river basin
management. The GREAT-ER software calculates the distribution of predicted
environmental concentrations (PECs) of consumer chemicals in surface waters.
Compared with other regional generic models, realism is increased within
GREAT-ER by incorporating spatial and temporal characteristics of the receiving
environment in the models and underlying databases (Fig. 4). The design of the
GREAT-ER system has been approached in a modular way containing: the data
56 N. Suciu et al.

Diffusive mass transfer Stratosphere
Non-diffusive mass transfer Air
Troposphere
Emission
dry deposition
Air Boundary wet deposition
precipitation
dry deposition
Layer
wet deposition (air, aerosol)
precipitation
dry deposition
wet deposition

Litterfall
Plant Foliage Surface Soil
particle washoff
(air, water, solid) (air, water, solid)
Surface Water vegetation xylem flow
phleom xylem leaching flow Soil
(pure water, suspended flow flow
solid, biota) Vadose Soil
Root Zone root decay
(air, water, solid)
(water, solid)

settling resuspension water runoff and solid runoff
leaching flow

interflow
Sediment Ground Water Zone
baseflow (water, solid)
(water, solid)
burial

Fig. 3 The MCM domains and fate mechanisms incorporated into CHEMGL [38]

Table 3 Principal characteristics of CHEMGL model (based on [38])
Principal characteristics Multimedia model for fate and exposure analyses of chemicals
Impact categories Ecotoxicological effects
Exposure routes Not considered
Fate, exposure and effect Fate and exposure of chemicals considered
Chemical considered Organic chemicals
Media considered Air (free troposphere, stratosphere), water (surface and ground
water), soil (two layers), sediment, vegetation (plant foliage
and plant route)
Spatial variation Local scale
Source code availability Yes, equations available
Model availability Yes
Dynamic or steady-state Both steady an unsteady state considered
Availability for sensitivity and Not considered
uncertainty analyses
Population category Not considered

manipulation module, hydrology module, the waste pathway and river modelling
module and the end-user desktop GIS module [60].
In the data manipulation module, input data sourced from several databases and
from the hydrology module are transformed into appropriate geographical informa-
tion system (GIS) formats [61]. Before that, the hydrology module combines
several hydrological databases with a hydrological model, providing to the
Environmental Fate Models 57

Fig. 4 GREAT-ER – refinement of generic regional exposure models, by taking into consider-
ation actual discharge pathway, river flow and waste water treatment plant (WWTP) (as described
by Schowanek and Webb [59])

GREAT-ER system the required river flow distributions, flow velocities and river
characteristics.
The waste pathway and river modelling module is used for the prediction of
chemical emission, of chemical removal/transformation during conveyance and
treatment, and of chemical fate in rivers [62]. Chemical fate in wastewater treat-
ment plants (WWTP) and in rivers is described deterministically, with several
levels of complexity being available to reflect the available information concerning
both the chemical and the environment.
In the last module, the end-user desktop GIS, access to and visualization of the
databanks and model results is achieved, as well as the linking of the models with
the data banks. The GIS databanks, the waste pathway models and the river models
are integrated into one coherent simulation system. Such integration process results
in an operational end-user system, which runs on a PC platform. The hydrological
models and the ARC/INFO spatial data processing steps are not integrated into the
end-user software system. The user interface is the front-end between the user and
the software system. It allows the selection of catchments, chemicals as well as the
input of model and scenario parameters. The user interface also handles filtering
and visualization of model results by the GIS. Avenue (ESRI®) has been used for
the development of this interface in an ARCVIEW (ESRI®) environment.
ARCVIEW® 3.0a or 3.1 software is required to run GREAT-ER. Furthermore, a
variety of river catchments in the EU are available to the user or under development
(www.great-er.org).
In Table 4 an overview of the principal characteristics of GREAT-ER model is
presented.
58 N. Suciu et al.

Table 4 Principal characteristics of GREAT-ER model (based on [60])
Principal characteristics Aquatic chemical exposure prediction tool
Impact categories Ecotoxicological effects
Exposure routes Not considered
Fate, exposure and effect Fate and exposure of chemicals in surface water
Chemical considered Organic and inorganic chemicals
Media considered Not considered
Spatial variation Regional scale
Source code availability Yes
Model availability Yes
Dynamic or steady-state Steady-state
Availability for sensitivity and uncertainty Yes
analyses
Population category Not considered

3.5 SimpleBox Model

SimpleBox is a nested multimedia environmental fate model in which the environ-
mental compartments are represented by homogeneous boxes. It consists of five
spatial scales; a regional scale, a continental scale and a global scale consisting of
three parts, reflecting arctic, moderate and tropic geographic zones (Fig. 5)
SimpleBox is a generic model, it can be customized to represent specific envi-
ronmental situations. In its default setting, the SimpleBox computation represents
the behavior of micropollutants in a regional and continental scale, representing a
densely populated Western European region, and the whole European Union,
respectively. SimpleBox follows the Mackay concept of sequentially carrying out
the modelling procedure at different stages of complexity of “levels” [56]. The
model allows to perform the non-equilibrium, steady-state computation, as well as
the quasi-dynamic non-equilibrium, non-steady-state computation.
Whereas the fugacity approach was used by Mackay for the computation of mass
flows and the concentration levels, the SimpleBox adopt the concentration-based
“piston velocity” type mass transfer coefficients (ms1). This is, mainly, because
most scientific papers express the mass transfer in these terms, rather than in terms
of the fugacity-based “conductivity” type coefficients (mol h1 Pa1). Furthermore,
the transfer and transformation phenomena are treated as simple pseudo first-order
processes, similar to Mackay models.
The environmental compartments are represented by boxes and the concentra-
tion of a chemical in these boxes is affected by processes that cause mass flows of
the chemical to and from the boxes. The chemical can be input into a box from
outside the system, output from a box to outside the system, or transported by
means of advective or diffusive processes to and from other boxes. A mass balance
equation can be written for each of the boxes representing the mass flow of the
chemical. Generally, the magnitude of these mass flows depends on the concentra-
tion of the chemical in the boxes. If mathematical expressions which relate the mass
flows to the concentrations are available, the set of mass balance equations (one for
Environmental Fate Models 59

GLOBAL SCALE

CONTINENTAL SCALE

REGIONAL SCALE

ARCTIC ZONE MODERATE ZONE TROPIC ZONE

Fig. 5 SimpleBox 2.0 model

Table 5 Principal characteristics of SimpleBox model (based on [63])
Principal characteristics Nested multimedia environmental fate model
Impact categories Ecotoxicological effects
Exposure routes Not considered
Fate, exposure and effect Just the fate of chemicals is considered
Chemical considered Organic chemicals
Media considered Air, water, soil, sediments and vegetation
Spatial variation Regional, continental and global scale
Source code availability Yes
Model availability Yes
Dynamic or steady-state Steady-state and quasi-dynamic
Availability for sensitivity and uncertainty Not considered
analyses
Population category Not considered

each box) can be solved. Therefore, the concentrations in each of the boxes can be
computed.
An overview of the principal characteristics of the SimpleBox model is given in
Table 5.

3.6 BETR Model

The BERT model is based on the fugacity concept and exploits existing contami-
nant fate modelling techniques. The BERT model is built on a general framework
that links individual regional contaminant fate models to create a model that
encompasses a larger, spatially heterogeneous area. It can thus address issues of
long-range transport of chemicals between regions within the continent [64].
Background concentrations can be specified to include advective inflow of
chemical in air or water from outside the model area, or the regional environments
60 N. Suciu et al.

can be linked into a closed system. Thus the framework is capable of describing
contaminant fate on specific national, continental, or even global scale. Appropriate
boundary conditions must, of course, be selected for each system. Models of larger
geographic areas are built up from box models of chemical fate in smaller regions,
with regional boundaries selected to account for considerations such as geographic
features, political boundaries and chemical use patterns. The BERT model, for
example for North America, is composed of 24 linked regional environments with
boundaries based on geographic features, principally watersheds and soil types.
In the BERT model, the environment in each region is described as a connected
system of seven discrete, homogeneous compartments. Describing the environment
in this fashion is a characteristic of multimedia environmental models, and all
models of this type use a similar approach, as already specified in the previous
described models. Furthermore, the number of compartments considered in existing,
and partially described in this chapter, models varies from two, for simple aquatic
fate or air–soil interaction models, to about 10 for models of regional environments
that include different soil and water types in individual regions. Figure 6 illustrates
the seven compartment regional environment of the BETR model framework
whereas in Table 6 are given its main characteristics.

3.7 CalTOX

The CalTOX model was originally developed as a set of spreadsheet models and
spreadsheet data sets for assessing human exposures from continuous releases to
air, soil, and water [7]. Hertwich [65–67] applied the CalTOX model for the
assessment of human toxicity in Life Cycle Assessment (LCA). Ecotoxicicity is
not evaluated in the model.
The current version of CalTOX (CalTOX4) is an eight-compartment regional
and dynamic multimedia fugacity model. CalTOX comprises a multimedia transport
and transformation model, multi-pathway exposure scenario models, and add-ins to
quantify and evaluate variability and uncertainty. To conduct the sensitivity and
uncertainty analyses, all input parameter values are given as distributions, des-
cribed in terms of mean values and a coefficient of variation, instead of point
estimates or plausible upper values.
Sub-systems included in CalTOX refer to the prediction of the fate, the exposure
and the effect. Next, a brief description of these sub-systems is given:
• Fate and exposure analyses. The multimedia transport and transformation model
is a dynamic model that can be used to assess time-varying concentrations of
contaminants that are placed in soil layers at a time-zero concentration or
contaminants released continuously to air, soil, or water. This model is used for
determining the distribution of a chemical in the environmental compartments.
An overview of the partitioning among the liquid, solid and/or gas phases of
individual compartments is presented in Fig. 7. The exposure model encompasses
Environmental Fate Models 61

n+1 n+1

ΣD1(j,1)
j –1
(1) Upper Air Detrat
Σj –1
D1(i,j)

E(1) 1 ,3) 1,6) 1,4) 1 ,2) 1,5)
D( D( D( D( D( Drxn(1)

n+1

ΣD2(j,i)
n+1

j –1
(2) Lower Air D(
2,
1)
5)
ΣD2(i,j)
j –1
2,3) 2 ,6) 2 ,4) (2,
E(2) D( D( D( D
Drxn(2)

E(3)
(3) Vegetation
D( )
3,
2) 3,6
D(
Drxn(2)

E(6) (6) Soil D( n+1

ΣD4_5(i,j) ΣD4(i,j)
D( n+1
6, 6,
Drxn(6) 3) 2) D(
Dadv(6) D(6,4) 4, E(7)
2) j –1 j –1
D(4,5) D( n+1

n+1 (4) Fresh )
5,
2) ΣD5(i,j)
ΣD4(j,i)
j –1
Water
4,7
D( Drxn(4)
(5) Coastal
j –1
n+1

ΣD4_5(j,i)
E(4) Water j –1
(7) n+1

Sediment
D(
7,
4)
Drxn(5)
ΣD5(j,i)
j –1
E(7) Dadv(7) Drxn(7)

lntercompartmental Transfer Advection Emissions Degradation

Fig. 6 Environmental compartments and contaminant fate processes in region “i” of the BETR
linked regional model framework as described by MacLeod et al. [64]

Table 6 Principal characteristics of BETR model (based on [64])
Principal characteristics Multimedia environmental fate model
Impact categories Ecotoxicological effects
Exposure routes Not considered
Fate, exposure and effect Just the fate of chemicals is considered
Chemical considered Organic chemicals
Media considered Air, water, soil, sediments and vegetation
Spatial variation Regional, continental and global scale
Source code availability Yes
Model availability Yes
Dynamic or steady-state Steady-state and dynamic
Availability for sensitivity and uncertainty analyses Not considered
Population category Not considered

23 exposure pathways through inhalation, ingestion of foods and dermal contact.
They are used to estimate average daily doses within human population linked
geographically to a release region. More information characterizing this type of
models are given in the next chapter.
• Effect analysis. The CalTOX scheme can calculate cancer and non-cancer
human toxicity potential (HTP) values for air and surface water emissions of
330 compounds. However, more information concerning the HTP and toxicity of
a compound are available in the next chapter.
62 N. Suciu et al.

Fig. 7 Overview of the partitioning among the liquid, solid and/or gas phases of individual
compartments [8]. Note: In the current version of CalTOX (CalTOX4), the plant compartment
comprises two sub-compartments [plant surfaces (cuticle) and plant leaf biomass (leaves)]

The main characteristics of the CalTOX model are presented in Table 7.

3.8 XtraFOD Model

The XtraFOOD model was developed within the framework of a research project
initiated by the Flemish Institute for Technological Research (VITO) [69]. The
model calculates transfer of contaminants in the primary food chain (Fig. 8). In the
project, the transfer model was coupled with historical food consumption data to
estimate human exposure to contaminated food products. The model focuses on the
terrestrial food chain. The XtraFOOD model consists of three modules, which are
inter-linked:
• A mass balance model at the farm level: Calculation of inputs and outputs.
• Bio-transfer module: Calculation of the transfer of contaminants to vegetable
products (vegetables, cereals, animal feed) and animal products (meat, milk
dairy products, poultry, eggs).
• Exposure and impact module: Calculation of the exposure from food (and other
exposure routes) and comparison with reference values.
Environmental Fate Models 63

Table 7 Principal characteristics of the CalTOX (based on [68])
Principal characteristics Multimedia model for fate analysis and extensive analysis
of exposure pathways
Impact categories Human toxicity
Exposure routes Inhalation, ingestion and dermal contact
Fate, exposure and effect Fate, exposure and effect are considered
Chemicals considered Organic and inorganic compounds
Media considered Air, water, sediments, three soil layers, vegetation (two
sub-compartments)
Spatial variation Not considered
Source code availability Yes, as Excel spreadsheet
Model availability Yes
Dynamic or steady-state Dynamic
Availability for sensitivity and Yes
uncertainty analyses
Population category Not considered

Fig. 8 Overview of contaminant flows in a model agro-ecosystem to the food chain [69]

The XtraFOOD model calculates as output the food intake and resulting con-
taminant intake, independently for age and gender categories. Exposure can be
calculated as being representative for a population or separately for local and
background intake. All these intakes are linked to the model output. Additional
intakes are provided to add concentration data in non-farm-related foods (e.g. fruit
juice, fish, etc.).
An overview of the principal characteristics of the XtraFOOD model is given in
Table 8.
64 N. Suciu et al.

Table 8 Principal characteristics of the XtraFOOD model
Principal characteristics Multimedia model focused on the primary food
chain
Impact categories Human toxicity
Exposure routes Ingestion
Fate, exposure and effect Fate and exposure are considered
Chemicals considered Organic compounds and heavy metals
Media considered Air, soil, farm-related crops, animal
Spatial variation Not considered
Source code availability Not considered
Model availability Not specified
Dynamic or steady-state Steady-state
Availability for sensitivity and uncertainty Yes
analyses
Population category Age and gender are considered

3.9 2-FUN Tool

2-FUN tool is a new integrated software based on a multimedia model, physiologi-
cally based pharmacokinetic (PBPK) models and associated databases. The tool is
a dynamic integrated model and is capable of assessing the human exposure to
chemical substances via multiple exposure pathways and the potential health risks
(Fig. 9) [70]. 2-FUN tool has been developed in the framework of the European
project called 2-FUN (Full-chain and UNcertainty Approaches for Assessing
Health Risks in FUture ENvironmental Scenarios: www.2-fun.org).
The multimedia model present in the 2 FUN tool was developed based on an
extensive comparison and evaluation of some of the previously discussed multime-
dia models, such as CalTOX, Simplebox, XtraFOOD, etc. The multimedia model
comprises several environmental modules, i.e. air, fresh water, soil/ground water,
several crops and animal (cow and milk). It is used to simulate chemical distribu-
tion in the environmental modules, taking into account the manifold links between
them. The PBPK models were developed to simulate the body burden of toxic
chemicals throughout the entire human lifespan, integrating the evolution of the
physiology and anatomy from childhood to advanced age. That model is based on a
detailed description of the body anatomy and includes a substantial number of
tissue compartments to enable detailed analysis of toxicokinetics for diverse
chemicals that induce multiple effects in different target tissues. The key input
parameters used in both models were given in the form of probability density
function (PDF) to allow for the exhaustive probabilistic analysis and sensitivity
analysis in terms of simulation outcomes [71].
The environmental multimedia and PBPK models were built and linked together
on the common platform software called Ecolego® (www.facilia.se). One of the
main characteristics of Ecolego system is the use of Interaction Matrices to build and
visualize models (Fig. 10). The effective graphical simulation interface presented in
Environmental Fate Models 65

Fig. 9 Multi-pathways that substances can take to reach humans (the area enclosed by a dashed
line emphasizes the indirect pathways to humans via food chains) [70]

the Ecolego system can facilitate a comprehensive identification and visualization of
the exposure pathways and allow classification of the role of different environmen-
tal modules (subsystem) in terms of transfer relationship. In the Ecolego system,
advanced methods concerning probabilistic and sensitivity analyses can be selected:
(a) Monte Carlo methods for the propagation of parametric uncertainties; (b) an
optimization function to correlate input parameters with simulated outputs in the
Monte Carlo process and then to optimize the values of input parameters and
(c) several regression and Fourier tests for conducting sensitivity analysis [20].
The complete 2-FUN tool allows for realistic and detailed lifetime risk assess-
ments for different population groups (general population, children at different
ages, pregnant women), considering human exposure via multiple pathways such as
drinking water, inhaled air, ingested vegetables, meat, fish, milk, etc.
The main characteristics of the 2-FUN tool are described in Table 9. 2-FUN tool
has the following prominent features which differentiate it from other models.
• Its capability to conduct full-chain risk assessment on a common system, which
allows for linking the simulation of chemical fate in the environmental media,
multiple pathways of exposure and the detailed analysis for multiple effects in
different target tissues in human body (by PBPK models).
• Its capability to assess the health risk of specific human groups vulnerable to
toxicants, i.e. for woman, infant.
• It contains a wide range of methods for sensitivity and uncertainty analyses.
• It contains an exhaustive database of PDF for input parameters.
• It can be user-friendly because of its effective graphical simulation interface and
its flexibility, which facilitates users to design scenarios for target regions and
66 N. Suciu et al.

Inputs 1 to 2
Comp. 1

Inputs 2 to 3
Comp. 2

Comp. 3
Outputs 3 to 1

Fig. 10 The schematic of interaction matrix (left) and representation of the interaction matrix in
the Ecolego system (right)

Table 9 Principal characteristics of 2-FUN tool [70]
Principal characteristics Integrated tool coupling an environmental multimedia
model and PBPK models
Impact categories Human toxicity
Exposure routes Ingestion, inhalation and dermal intake
Fate, exposure and effect Fate, exposure and potential effect are considered
Chemicals considered Organic and inorganic chemicals
Media considered Air, fresh water, soil/ground water, farm-related crops, and
animal (cow and milk)
Spatial variation Not considered (mainly used for regional scale)
Source code availability Yes
Model availability Yes in the near future
Dynamic or steady-state Dynamic
Availability for sensitivity and Yes
uncertainty analyses
Population category Age and gender are considered

arrange the tool on their ways, i.e., users can select only the environmental
modules necessary for their regional scenarios.

4 Conclusions

A large and growing volume of literature exists on multimedia models. They serve
an essential role as tools for bringing together information on chemical and
environmental properties with a view to estimating chemical fate. They can be
configured in various ways and can range greatly in complexity, but in principle it is
preferable to use the simplest model that can generate the desired result.
Mainly, the available models have been developed based on the fugacity approach,
which use the fugacity as surrogate of concentration, for the compilation and solution of
mass-balance equations involved in the description of chemicals fate. However, a new
Environmental Fate Models 67

approach based on Markov chain principle it starts being investigated for the develop-
ment of models able to estimate the environmental fate of chemicals.
Furthermore, there can be identified two opposing trends in model develop-
ment. One is a trend toward more detailed models with higher fidelity to the real
system, driven by the availability of highly resolved environmental data,
increases in computer power, and progress in atmospheric and earth sciences.
The other trend is toward models that are tailor-made to specific scientific
questions or decision-making problems, driven by the philosophy of parsimony
and the increase in the need for scientific results as a basis for decision-making in
modern society.
However, in the future, as in the past, models will be required to address a range
of interdisciplinary scientific questions about chemicals in the environment. Cer-
tainly, mass-balance models at different spatial and temporal scales and with
different levels of detail, including multimedia models based on the unit world
approach, will continue to be essential tools in research, education and decision
support in the future. In the last 30 years, models based on these principles have
accrued significant credibility by providing insights into many key problems in
environmental chemistry. These tools are now well established and mature, and
available to study the new generation of environmental pollutants. The principles
that have been developed for mass-balance models of chemical substances also
stand ready to be adapted to address emerging challenges including supporting the
development of green chemistry, addressing engineered nanomaterials, which are
of increasing economic importance and behave differently from the common
chemicals.
Therefore, 30 years after the establishment of the field, we believe multime-
dia environmental contaminant fate modelling remains a vibrant scientific
discipline that has a central role in science and decision-making in environmen-
tal chemistry.

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Toxicological and Ecotoxicological Studies
for Additives

Nazanin Golbamaki Bakhtyari, Diego Baderna, Elena Boriani,
Marta Schuhmacher, Susanne Heise, and Emilio Benfenati

Abstract As the world has become ever more industrialized, an alarmingly large
number of chemicals have entered as contaminant mixtures in waste, air, water, and soil.
The need to decrease costs and reduce animal suffering for chemical risk
assessment has ever more encouraged the use of methods alternative to the use of
animals to predict toxicity. These alternative methods can be generally divided into
two subgroups: study of toxicity in laboratory tubes on small organisms (in vitro)
and computational techniques (in silico).
These techniques have recently become more important due to mandates such as
the categorization of the Canadian Domestic Substance List [Canadian Domestic
Substance List; Canadian Environmental Protection Act, 1999 (Section 74, CEPA
1999)], the European Union’s REACH [REACH; REGULATION (EC) No 1907/2006
of the European Parliament and of the Council of 18 December 2006 concerning the
Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH),
establishing a European Chemicals Agency, amending Directive 1999/45/EC and
repealing Council Regulation (EEC) No 793/93 and Commission Regulation (EC)
No 1488/94 as well as Council Directive 76/769/EEC and Commission Directives
[91/155/EEC, 93/67/EEC, 93/105/EC and 2000/21/EC], and Cosmetics Regulations
[European Union’s Cosmetics Regulations; REGULATION (EC) No 1223/2009 of the
European Parliament and of the Council of 30 November 2009 on cosmetic products],
the Japanese Chemical Substance Control [Japanese Chemical Substance Control

N.G. Bakhtyari (*), D. Baderna, E. Boriani, and E. Benfenati
Laboratory of Environmental Chemistry and Toxicology, Mario Negri Institute,
Via Giuseppe La Masa 19, 20156 Milan, Italy
e-mail: nazanin.golbamaki@marionegri.it
M. Schuhmacher
Environmental Analysis and Management Group, Departament d’Enginyeria Quı́mica,
Universitat Rovira i Virgili, Av. Paı̈sos Catalans 26, 43007 Tarragona, Spain
S. Heise
Hamburg University of Applied Sciences (HAW-Hamburg), Lohbrügger Kirchstraße 65,
21033 Hamburg, Germany

B. Bilitewski et al. (eds.), Global Risk-Based Management of Chemical Additives II: 73
Risk-Based Assessment and Management Strategies, Hdb Env Chem (2013) 23: 73–90,
DOI 10.1007/698_2012_193, # Springer-Verlag Berlin Heidelberg 2012,
Published online: 22 September 2012
74 N.G. Bakhtyari et al.

Act on the Evaluation of Chemical Substances and Regulation of Their Manufacture,
etc. (Act No. 117 of October 16, 1973 amended in 2009)], as well as their continued use
by the U.S. Environmental Protection Agency (EPA) [Kavlock R, Dix D. J Toxicol
Environ Health B Crit Rev 13(2–4):197–217, 2010] and U.S. Food and Drug
Administration (FDA) [U.S. Environmental Protection Agency (EPA) and U.S. Food
and Drug Administration (FDA); TSCA (1976) Toxic Substances Control Act. United
States Publ. Law 94–469, 90 Stat 2003, USA].
Day by day, the number of scientific works and techniques based on in vitro tools
has increased their relevancy, supporting the hypothesis of the use of in vitro
models as refinement technique due to their ability to provide information on
central events involved in toxicant mode of action.
In vitro tools could be used alone or in test batteries with increased potency of the
description of cellular events and changes. The chapter provides a brief introduction
on the components of an in vitro system, the main differences between models for
research and models for testing and a list of validated alternative methods according
to the European Centre for the Validation of Alternative Methods (ECVAM) (http://
ecvam.jrc.it/, http://ecvam.jrc.ec.europa.eu/) evaluation.
Furthermore, in recent years more and more studies have been carried out in
which computational programs have been used to predict the toxicity of chemical
compounds. The main driving force behind this trend has been the emergence of
new chemical descriptors, algorithms, and statistical perspectives, in addition to the
higher expectations as to how such programs can have specific applications, such as
for regulatory purposes or drug discovery (Benfenati E. Chem Cent J 1:32, 2007).
The performance of the computational models discussed in this chapter relates to
the chemical information available and nature of mathematical algorithms.
Obtaining a good quality QSAR model depends on many factors, such as the
quality of biological data and the choice of descriptors and statistical methods. As
a consequence, the uncertainty of the QSAR-predictions is a combination of
experimental uncertainties and model uncertainties (Computational chemistry:
risk assessment for pharmaceutical and environmental chemicals, edited by Ekins
S, WILEY Series on Technologies for the Pharmaceutical Industry, 2007). In this
chapter we will consider the applications of QSAR models, and see how
interactions are possible between different computational techniques, as well as
in vivo and in vitro methods.

Keywords Alternatives to animal testing, Computational toxicology, In silico,
In vitro, Predictive models, QSAR models, Regulation

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
1.1 In Vitro Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
1.2 In Silico . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
2 Considerations on the Applicability of the Alternative Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
Toxicological and Ecotoxicological Studies for Additives 75

1 Introduction

The requirements arising from the regulation and the need to better characterize the
toxicological, eco-toxicological and environmental properties of an increasing
number of chemicals have the consequence of an increased number of animal
experiments, to provide answer to these data needs [1].
However, this request of more animal testing faces several issues. There is an
ethical concern on the millions of animals used every year for experiments. These
tests are also highly expensive. Thus, this poses questions about the costs for these
experiments and the resources available to cover them. Many of these tests,
especially those chronic, require a long time, years in some cases. The number of
available laboratories in Europe to cover this potential request is insufficient.
For all these reasons, some European regulations foresee the use of methods
alternative to animal testing, such as the REACH legislation [2], and actually the
cosmetics directive [3] foresees the complete ban of animal tests for cosmetics
by 2013.
Alternative tests can be divided into two categories: in vitro and in silico. In vitro
methods refer to the fact that experiments are done in a tube, generally. In silico
methods refer to the use of the computer to model a certain property of interest.
Below, we will analyze these two categories, and which criteria can be used to
choose a suitable methodology.
The term alternative includes “all procedures which can completely replace the
need for animal experiments, reduce the number of animals required, or diminish the
amount of distress or pain suffered by animals in meeting the essential needs of man
and other animals.” Its purpose is to promote the development and implementation
of new methods to Replace, Reduce, Refine (the “3 Rs”) animal testing with modern
alternative approaches. Russell and Burch [4] proposed the framework of the 3 Rs
more than 40 year ago. The authors proposed that all research using animals should
be evaluated to see if the 3 Rs could be applied. Since that landmark publication,
significant progress has been made, especially in the arena of regulatory testing [5].
An important point made by the ECVAM is that these three aspects should
not be considered as alternatives that could replace each other, but as parts of an
integrated system which should lead to progress in the development of non-animal
tests and testing strategies.
Non-animal tests therefore comprise:
1. Maximizing the use of existing information, including the reasons for producing
a chemical and its uses, as well as knowledge of its toxic hazard potential.
2. The use of data concerning the physicochemical properties of chemicals (e.g.,
stability, solubility, pH, octanol-water partition coefficient, and protein binding).
3. Predictions based on structure–activity relationships (SARs), including qualita-
tive and quantitative mathematical models, and the use of read-across data from
related chemicals.
76 N.G. Bakhtyari et al.

4. The biokinetic modeling of physiological, pharmacological, and toxicological
processes.
5. Experiments on lower organisms not classed as “protected animals” (bacteria,
fungi, plants, invertebrate animals).
6. Studies on vertebrates at early stages of development (before they become
protected animals).
7. Studies on in vitro systems of various kinds (including whole perfused organs,
tissue slices, cell, tissue and organotypic cultures, and sub cellular fractions).
8. Human studies (including estimations of occupational and environmental expo-
sure, epidemiological investigations, post-marketing surveillance for medicines,
cosmetics and household and agricultural products, and the ethical and properly
controlled use of human volunteers) [6].

1.1 In Vitro Tests

In the last 30 years, the use of in vitro tools for toxicological studies and evaluation
has become relevant and the number of scientific works and techniques has
increased day by day. One of the most important advantages of in vitro systems
is their ability to serve as model for the central events in the in vivo toxicological
process, and a depth evaluation of the intrinsic cellular toxicity can provide useful
information for toxicological safety evaluation.
An in vitro toxicity system is made by three components:
– The biological models
– The endpoint and the method to measure it
– The protocol
The biological model consists of the biological systems which will be used and its
specific culture conditions. Organ cultures, tissue slices, primary cells, cell lines, sub
cellular organelles, macromolecular system and prokaryotic, fungi or plant culture
are the most used biological components. The ability of the biological model to
produce accurate, valid, and usable data for a possible in vivo extrapolation depends
on the similarity of the same system with the cellular phenotype to model: for
example, primary alveolar cells or lines derived from lung tumors are more relevant
and suitable for inhalation toxicity studies comparing to intestinal cells.
Specific culture conditions are essential to ensure that the biological model
maintains unchanged, as long as possible, its intrinsic characteristics in terms of
biological response and cell function.
The endpoint is the final effect to be measured within the biological system after
the exposure to chemicals. Referring to in vitro systems, it is generally a type of
biological response such as the release of an enzyme, the activation of a pathway,
changes in the cell cycle or death. The measurement of the endpoint allows defining
the concentration–response relationship in the used system. The specificity of the
endpoint is a fundamental key point to make a biological system more useful in
obtaining relevant information on mechanistic basis of the chemical–cell
interactions.
Toxicological and Ecotoxicological Studies for Additives 77

Also, the test procedure (protocol) is fundamental because it allows comparing
results from different laboratories and from different experimental sets. Moreover,
selected test protocol could affect the interpretation of the results, the information
content and its application in the safety evaluation process, as stated by Frazer
“if the biological system is exposed to a test chemical for 24 h and the endpoint
assay is immediately conducted, the data produced would be most relevant to the
acute toxicity of the test material. If, on the other hand, the system is exposed to
material for 24 h and the system is cultured in the absence of the test material for
additional 48 h before the endpoint assay is conducted, the data would be more
relevant to recovery from toxicity rather than acute toxicity” [7].
Analyzing the use of models, it is possible to underline that in vitro systems are
mainly used for research and for testing/screening of compounds. In the first case,
these tools are employed to test hypothesis and the experimental model is chosen
taking into account the nature of the hypothesis to be tested.
The final goal of models used for “testing” or “screening” is to verify whether a
special condition or feature is present or not. In this case the model system should
be selected a priori based on scientific consensus and the testing protocols must be
standardized in order to obtain comparable values when the same test is performed
by two different laboratories or operators. Moreover, the existence of standardized
methodologies could be very useful for regulators which need a certain degree of
reliability to make appropriated decisions.
This is the main difference between models for research and for testing but
in some cases, especially in the environmental sector and in the screening of
chemicals, it is very difficult to establish the dividing line between these two
realities. According to Frazier, what is important is to verify the adequacy and
the specificity of the model system to answer the posed question.
Focusing on testing purpose, it is possible to classify the models into three
categories:
– Screens: used to obtain preliminary information sufficient to make limited
management decisions.
– Adjuncts: are often integrated part of regulatory evaluation strategies, but
usually the derived information is not sufficient to support a final safety decision.
– Replacements: are in vitro tests able to completely replace the use of in vivo
toxicity test in a specific area of toxicity testing.
In vitro tools could be used alone or in test batteries. Multiple endpoint batteries
increase the power of the evaluation because they provide information of different
cellular functions. This information can be useful to investigate the mode of action
of toxicity and to provide data regarding the mechanistic nature of the toxicological
effects of the chemical [8].
In spite of the great effort and advances made on in vitro testing, we are still far
to have alternative methods robust enough to cover developmental, neurotoxic,
reproductive, or carcinogenic potential for the substances evaluated. However the
use of some distinct approaches may cover a great part of the potential toxic effects
of some environmental pollutants.
78 N.G. Bakhtyari et al.

Focusing on validation process of in vitro methods, it is possible to underline
some differences between tools for research and ones for toxicological testing.
A research model is validated when there are some specific evidences confirming
that the information from the model is able to correctly describe the process in the
intact animal. Tools for toxicity testing are often used to evaluate safety hypothesis
so they can be used without requiring in vivo confirmation. They are validated using
a subset of well-known materials and, once validated, systems will be applied to
new unknown materials or mixtures in order to evaluate their toxicity and compare
their potential with other chemicals.
In both cases, the validation process could be divided into two components:
reliability and relevance. Reliability (precision) is the ability of the method to obtain
reproducible results between laboratories while relevance (accuracy) is defined by
the comparison of the output from the applied method with the ones obtained using a
“gold standard” test which works as a reference at international levels.
ECVAM as part of the JRC fulfills the task to validate alternative methods. Its
advisory group ESAC advises ECVAM scientifically and gives expert judgment on
the different proposed non-animal tests.

1.1.1 Advantages and Disadvantages of Using In Vitro Methods

The advantages of these methods are that they are generally short-term tests giving
results in few hours or days, they require only small amount of chemical and space
and they are generally cheap to run compared to in vivo experiments.
On the other hand, it is often very difficult to relate a response to a specific
concentration because it is difficult to keep the concentration constant in such
systems, for example in the presence of plastic materials and media with high
content of other organic compounds. Moreover toxico-kinetics aspects such as
distribution in different compartments are also lacking information in these models.
The disadvantages of these methods are that they only reflect part of what is
going on inside the specific tissue or enzymatic process and thus do not take
degradation in the whole organism into consideration or other processes that may
influence the same process in an intact organism [9].
A survey of the regulatory status is given in Table 1, indicating those in vitro
procedures that are accepted by EU, OECD [10], and/or the USA (based on http://
www.ccac.ca; http://ecvam.jrc.ec.europa.eu/). However, there are methods that are
scientifically validated reported by ECVAM, but still not properly accepted for
regulatory purposes. This is the case of carcinogenicity (non-genotoxic, e.g., Three
Cell Transformation Assays (CTA) using Syrian hamster embryo cells (SHE) and
the BALB/c 3T3 mouse fibroblast cell line for in vitro carcinogenicity testing),
monoclonal antibodies production, haematotoxicity and reproductive toxicity.
Toxicological and Ecotoxicological Studies for Additives 79

Table 1 In vitro procedures that are accepted by EU, OECD and/or the USA
Endpoint Non-animal testing method Validation/regulation
Acute aquatic Fish acute toxicity – UTC-step-down EU
toxicity approach
Fish embryo toxicity (FET) test OECD – Assessing
evaluation
Acute oral toxicity Up-and-down procedure for acute oral EU
toxicity testing
Acute toxic class method for acute oral EU
toxicity testing
Fixed dose procedure for acute oral toxicity EU
testing Fixed dose procedure for acute oral
toxicity testing
Neutral red uptake (NRU) test with human US
cells
Neutral red uptake (NRU) test with rodent US
cells
Eye irritation Isolated chicken eye test EU
US
The bovine corneal opacity and permeability EU
(BCOP) and the isolated chicken eye US
(ICE) test methods for eye irritation
Hen’s egg test – chorioallantoic membrane EU/US: not
(HET-CAM) test method sufficiently
validated
Isolated rabbit eye (IRE) test method EU/US: not
sufficiently
validated
Slug mucosal irritation (SMI) assay EU: is being
evaluated
Chromosomal Micronucleus test as an alternative to the EU; OECD
aberration in vitro chromosome aberration assay for
genotoxicity testing
Genotoxicity Bacterial reverse mutation test (Ames test) OECD, US:
Approved
Saccharomyces cerevisiae gene mutation OECD
assay
Saccharomyces cerevisiae mitotic OECD
recombination assay
In vitro mammalian chromosome aberration OECD, US
test
In vitro mammalian cell gene mutation test OECD, US
In vitro sister chromatid exchange (SCE) test OECD
In vitro unscheduled DNA synthesis (UDS) in OECD
mammalian cells test
Monoclonal In vitro production of monoclonal antibodies EU
antibody
production
Haematotoxicity The colony forming unit-granulocyte/ EU
macrophage (CFU-GM) assay for
predicting acute neutropenia in humans
(continued)
80 N.G. Bakhtyari et al.

Table 1 (continued)
Endpoint Non-animal testing method Validation/regulation
Phototoxicity 3T3 neutral red uptake (NRU) phototoxicity EU, OECD
Pryrogenicity Five in vitro pyrogen tests EU, US
Reproductive and Embryonic stem cell test (EST) for EU
developmental embryotoxicity
toxicity Micromass (MM) embryotoxicity assay
Whole rat embryo embryotoxicity assay
Extended one-generation reproduction OECD: new test
toxicity study guideline
Combined repeated dose toxicity study with OECD
the reproduction/developmental toxicity
screening test
Micromass embryotoxicity assay EU
Whole rat embryo embryotoxicity assay EU
Frog embryo teratogenesis assay – Xenopus Not sufficiently
(FETAX) validated
EST-1000 method for skin corrosivity testing EU
SkinEthic™ human skin model for skin EU
corrosivity testing
CORROSITEX assay for skin corrosivity EU, US
Skin corrosion EpiDerm™ skin corrosivity test
EPISKIN™ skin corrosivity test EU, US
Rat transcutaneous electrical resistance EU, US
(TER) skin corrosivity test
Two in vitro skin irritation tests: EpiDerm SIT EU
and SkinEthicTM RHE assay
Artificial skin models (EpiSkin®, EpiDerm®) EU
for skin irritation testing
Reduced local lymph node assay (rLLNA) for EU, US
skin sensitization
Skin irritation Local lymph node assay for skin sensitization EU, US
(LLNA)
The relevance of the target-animal safety test EU
for batch safety testing of vaccines for
veterinary use
Skin sensitization ELISA test for batch potency testing of EU
erysipelas vaccines
ELISA test for batch potency testing of EU
tetanus vaccines for human use
Vaccines ELISA test for batch potency testing of EU
tetanus vaccines for human use

1.2 In Silico

The use of computational techniques to predict toxicity, or in silico approaches,
aims to decrease costs and reduce animal suffering for chemical risk assessment.
Toxicological and Ecotoxicological Studies for Additives 81

These techniques may be coarsely classified into techniques that mimic human
reasoning about toxicological phenomena (Expert Systems) and methods that
derive predictions from a training set of experimentally determined data (Data
Driven Systems).
Expert Systems attempt to formalize the knowledge of human experts, who
assess the toxicity of a new compound, in a computer program [11].
This approach is intuitively appealing to most users, because it promises easy
access to toxicological knowledge, and some of the most used predictive toxicology
software tools are in fact Expert Systems [e.g., Derek Nexus (https://www.
lhasalimited.org/) and Toxtree (http://toxtree.sourceforge.net/)].
Data Driven Systems are formalized methods for the extraction of prediction
models directly from experimental data. These systems vary in sophistication from
the relatively simplistic approach of forming chemical groupings (read-across and
grouping) to the more complex development of SARs [Qualitative identification of
chemical substructures with the potential of being reactive or toxic; the SAR model
investigates the existence of a relationship between a certain chemical property, such
as a fragment, and the effect, such as carcinogenic effect, without assigning a
numerical continuous value to the toxicity (http://ecvam.jrc.it/; http://ecvam.jrc.ec.
europa.eu/)] and QSARs (quantitative prediction of relative reactivity or toxicity) [12].
The non-testing method called read-across implies the use of endpoint informa-
tion for one chemical, called a “source chemical,” to make a prediction of the same
endpoint for another chemical, called a “target chemical.” The source and target
chemicals are considered to be similar in some way, usually on the basis of
structural similarity. It is assumed that, in general, similar compounds will exhibit
similar biological activity. In principle, read-across can be applied to characterize
physicochemical properties, fate, human health effects and ecotoxicity, and it may
be performed in a qualitative or quantitative manner, depending on whether the data
being used is categorical or numerical in nature [13, 14]. To estimate the properties
of a given substance, read-across can be performed in a one-to-one manner (one
analogue used to make the estimate) or in a many-to-one manner (two or more
analogues used) (http://toxtree.sourceforge.net/).
The reliability of read-across depends on the selection of appropriate analogues
associated with the availability of reliable experimental data. In some cases, it is
only possible to identify a limited number of suitable analogues, whereas in other
cases, it is possible to build up a larger and more robust chemical group, called a
chemical category. A chemical category is a group of chemicals whose physico-
chemical and human health and/or environmental toxicological and/or environmen-
tal fate properties are likely to be similar or follow a regular pattern as a result of
structural similarity (or other similarity characteristic). The presence of common
behavior or coherent trends in the chemical category is generally associated with a
common underlying mechanism of action. In general, the application of read-across
between analogues in a chemical category is considered to be more reliable than the
application of read-across in a smaller group of analogues (in which trends are not
apparent) [15].
82 N.G. Bakhtyari et al.

There are software that use more approaches for the prediction of toxicity; expert
systems, QSAR, and read-across (http://www.insilico.eu/use-qsar.html).
Here we will address in particular QSAR, being more used. However, the idea is
to extract the common criteria for all in silico methods.

1.2.1 QSAR, and SAR Models

QSAR means quantitative SAR. It is a model that relates the chemical structure to
an activity. In the so-called SAR the quantitative aspect of the phenomenon is not
addressed, and the study refers to categories, such as “toxic” and “non toxic.” In a
certain way, this is a simplified version of the QSAR model. The expression QSAR
sometimes covers both cases. If the modeled feature is a property, the expression
QSPR is also used.

1.2.2 The Components of the QSAR Models

The basic hypothesis of a QSAR model is that the activity (or effect or property) can
be put in relationship with the chemical, using some parameters to describe the
chemical. Thus, the three main components of the QSAR model are: the activity to
be modeled, the chemical information, and the way to establish a link between these
two components. For this, we need some suitable ways to describe the chemical and
a good mathematical algorithm.
Below we will analyze more in detail these three components of the QSAR
model.

1.2.3 The Chemical Information

There are two main ways to describe a chemical compound: using global descriptors,
or using specific fragments. Indeed, there are many QSAR models using global
descriptors, but there are also a certain number of them using fragments. Furthermore,
several models use both fragments and general descriptors.
Some simple global descriptors are: molecular weight, number of atoms present
in a molecule (e.g., number of chlorine atoms), number of double bonds, etc. Other
descriptors represent the ramification of the molecule. Certain descriptors take into
consideration the electronic charge on a certain atom, or its polarity.
Another kind of descriptors is the so-called physicochemical ones. They include
log P, lipophylicity, etc. Log P is the logarithm of the partition coefficient between
octanol water. This descriptor has been used since the first QSAR models, and
originally it was measured. Nowadays it is much more common to calculate it.
Nowadays there are thousands of molecular descriptors which have been
proposed.
Toxicological and Ecotoxicological Studies for Additives 83

1.2.4 The Modeling Algorithms: Classifiers and Regression Models

In the last decades not only thousands of chemical descriptors but also many
advanced, powerful modeling algorithms have been made available, The older
QSAR models were linear equations with one or a few parameters. Then, other
tools have been introduced, such as artificial neural network, fuzzy logic, and data
mining algorithms, making possible non linear models and automatic generation of
mathematical solutions.
We can distinguish the algorithms in two kinds: for the regressions and the
classification. Regression methods get a continuous value. Classifiers find the
category, for instance the toxicity class, of elements of a population.
Typically a QSAR model is built up starting with a set of chemicals with known
property values.
In some cases, especially in case of genotoxicity models, the human expert
identified fragments which can be related to the genotoxic effect. For instance, it is
known that nitrosoamines are genotoxic. The visual examination of a series of
chemicals sharing the same fragment may be used for this purpose. In this case the
effect is simply the toxic effect (genotoxic or not, for instance), and the chemical
information is simply the fragment. The algorithm is, in this case, the rule. Expert
systems have been built up in this way. Examples of this kind of models are
HazardExpert, Derek, and Toxtree.
More typically the process of building up the QSAR models requires more
complex chemical information. For a set of compounds, with known property
value, the descriptors are calculated. The process of model building proceeds through
a reduction of the molecular descriptors, in order to indentify the most important
ones. Then, using these selected chemical descriptors and a suitable algorithm, the
model is developed. Finally, the model so obtained has to be validated.
On the basis of the QSAR models there are three components: the toxicity
(or environmental) property of the chemicals, the chemical information associated
with these chemicals, and the mathematical function which links these two
components: the property and the chemical information.
Model development involves the use of chemical compounds with known
toxicity levels, which are then used as the training set. This is a very important
point since models can only be developed based on knowledge – and the bigger the
database the better the model. The model is subsequently developed using chemical
parameters and a suitable algorithm.
QSAR are rapidly evolving, for a series of advancements in the scientific field and
expectations as alternative methods. Indeed, new information technology techniques
have been introduced, and new ways to describe the chemical information, offering
new perspective, on the one hand, and on the other regulations, such as REACH, call
for the availability of robust models.
A few decades ago the range of chemical descriptors used was very limited.
Let us take the example of Corwin Hansch’s studies, in which he described
the relationship between ecotoxicity and a series of parameters, including log P
84 N.G. Bakhtyari et al.

(P ¼ partition coefficient between octanol and water). On the basis of this model,
toxicity could then be understood by quantifying uptake of the compound into the
fish’s body.
Over time other descriptors have been investigated in an attempt to better
explain certain factors, such as chemical reactivity and molecular size. Nowadays
thousands of chemical descriptors can be calculated and thousands of fragments can
be obtained using other programs.
The growth in the number of chemical descriptors and fragments is also the
result of the availability of more powerful modeling algorithms. The older QSAR
models used linear equations with a very limited number of parameters, in general
one or two. Multilinear regressions have now been developed, which offer the
possibility of screening a high number of parameters. Non-linear models and the
automatic generation of mathematical solutions have now been made possible by
the emergence of other tools such as artificial neural network, fuzzy logic, and data
mining algorithms.

1.2.5 Purposes in Predicting Models and Related Criteria

Regulatory models require not only powerful methods, but also certain characteristics
related to the intended use, such as use of suitable values as input of the model, great
consideration of the output of the model, which should fit into the format identified by
the law, with given thresholds and uncertainty, depending on the use, and other
features, such as transparency and reproducibility of the model.
The requirements for regulation may be different from those for other purposes.
Academic applications of QSAR models are the most typical. Here no strict
restrictions and needs exist, beyond the interests of the scientific community.
Models used within industry are also different. In this case, in most situations,
confidential data are used, and the interest is to avoid false positive, i.e. the industry
wants to avoid to make studies (and spend money) for chemicals which then result
to be non active (false positives).
Regulatory QSAR models are more demanding because of their relationship
with the law, which introduces requirements, some internal to the QSAR model
process, others external. Internally the model needs a high level of quality control.
Externally, the model has to comply with, and be suited for, the regulatory use.

1.2.6 Criteria for Evaluation of QSAR Models for Regulatory Purposes

Criteria which are suitable for regulatory purposes, to cope with a reduction of the
risk complying with the EU regulations, the REACH legislation provides a good
guidance on the requirements, since QSAR models are explicitly mentioned within
the law, in Annex XI.
Toxicological and Ecotoxicological Studies for Additives 85

According to REACH, a (Q)SAR is valid if:
• The model is recognized scientifically valid.
• The substance is included in the applicability domain of the model.
• Results are adequate for classification and labeling and for risk assessment.
• Adequate documentation of the methods provided.
Let’s discuss the first requirement, a criterion for us. We notice that it is not
requested that the model is validated. Validation is a formal process, which takes
many years. The formal validation process of a QSAR model would end after
REACH probably.
Thus, according to REACH the validity has to be assessed through scientific
criteria, considering the performance of the model in its results in prediction. Of
particular interest is the check for the predictive performance of the model.
For regulatory purposes greater attention should be given to models which avoid
false negatives. Thus, in the evaluation, preference should be given when the model
has lower false negatives.
The fact that the model works, that is predictive, should be quite obvious. It is
our opinion that this criterion should be applied to all in silico methods, not only
QSAR, and actually to all alternative methods. The same applies to all criteria listed
by REACH.
The second criterion is quite interesting. It requires demonstrating if the model,
which fulfills the requirements for the model, is appropriate for the chemical it has
been applied to. Thus, it is not enough to demonstrate that the model works. It is
assumed that it does not work in all cases. Thus, a specific evaluation has to be done.
There are some chemometric (chemometrics is a statistical area which combines
statistics and chemistry) tools which use the chemical descriptors and/or fragments of
the chemicals used to build up the model, and compare if the chemical descriptors
and/or fragments of the target chemical are similar. An example of this approach is
given by the freely available software AMBIT. A major disadvantage of this
approach is that it is based only on the chemical information.
Another recent tool has been developed within the ORCHESTRA project. The
tool keeps into account both the chemometric information and the toxicity
predictions done by the model, and in particular what kind of errors have been
done by the model. It applies to the CAESAR QSAR models. Furthermore, this tool
is based not only on the a priori data and information, as the other approaches,
but also on the a posteriori result of the model. The user knows if the model can or
cannot be used for a certain compound. In some cases a warning is given,
recommending expert opinion. In all cases the reasons for the reliability is given,
and it can be evaluated in a transparent way.
The third criterion is that the model should target an endpoint relevant for
REACH. Only models that address the endpoints of interest for REACH are
appropriate within this purpose. We notice that REACH mentions different
purposes for the QSAR models: classification and labeling, is one possible target
of the model, and risk assessment in another. In the first case models are classifiers;
in the second case a regression more is more suitable. Indeed, in the first case the
86 N.G. Bakhtyari et al.

output of the model is a class, while in the second one it is a continuous value.
A continuous value is necessary to get the ratio between the effect dose and the
exposure level.
The fourth criterion asks to transparency. This is reasonable, since all documen-
tation on the basis of the assessment of the properties of a chemical should be
clearly available and checkable. One of the driving forces of REACH was to have
the correct knowledge on the properties of the chemical substances on the market.
If some of the information is hidden, this clearly goes against the spirit of REACH.
Besides the criteria, we may identify other criteria, which are related to the
presence of desirable characteristics of the QSAR model.
QSAR models with a regulatory purpose should mimic the in vivo (and occa-
sionally, in vitro) data, which are typically used in the context identified by the law.
As a consequence it should be very much preferable that also the data on the basis of
the QSAR models are experimental data suitable for the regulation. In any case,
their quality should be very high, and a check should be done on it.
Furthermore, knowledge on the variability and uncertainty associated with each
component of the model should be addressed, and described. For any risk assess-
ment process, the uncertainty of the component is fundamental.
Another criterion is the model reproducibility. This refers in a certain extent to
the uncertainty, which was mentioned before, relatively to the knowledge on the
input parameters. Here we address the reproducibility of the final result.
Related to this is the easiness of the model. If we imagine a model which is
complicated, and has several parameters to be chosen, we may easily get different
results. Thus, ideally this is further criterion.
The clarity of the result should be another criterion. It may happen that the
output of the model is of difficult interpretation.
The access to the model is another criterion. Some models are free, others very
expensive.
The time necessary to get the results (speed of the model) is another desirable
criterion.
Another useful feature is the possibility to run predictions in batch, in order to
save time.
Other principles for the validation of QSAR models for regulatory purposes
were edited by OECD in 2007 [8]. A good model must have:
– A defined endpoint
– An unambiguous algorithm
– A defined domain of applicability
– Appropriate measures of goodness-of-fit, robustness and predictivity
– A mechanistic interpretation
The definition of the endpoint is essential to understand what kind of experi-
mental systems is being modeled by the in silico method.
The second principle is to ensure the transparency of the model, describing the
algorithms used to generate predictions. This information is critical to evaluate the
performance of the model. In the case of commercial models, the used algorithms
Toxicological and Ecotoxicological Studies for Additives 87

are not always made publicly available but the model’s reproducibility must be
explained in the guidance material.
The description of the applicability domain is needed to express the limitations
in terms of the types of chemicals; properties of mechanism can be generated by the
model with an acceptable reliability.
The information about internal and external validation for the model is used to
evaluate the performance of the in silico tool.
Regarding the last but not the least principle, it is recognized that it is not always
possible to provide a mechanistic interpretation of a given QSAR model but the
absence of this information does not preclude the use of the given model in the
regulatory context.
OECD also provides a check list for the application of its principles in the
context of QSAR validation. This checklist can be useful to help scientists and
regulators during the selection of a QSAR model and to evaluate its robustness/
validity [9].

2 Considerations on the Applicability of the Alternative
Methods

Some important general considerations should be done, to clarify the context of the
use of these alternative tools.
As it will be discussed later in this chapter, a number of regulatory initiatives
exist, dedicated to the validation of the alternative methods. However, the REACH
legislation clearly refers to “valid” QSAR methods, and not to “validated” methods.
Explaining this argument, Annex XI of REACH states the “scientific validity”
should be considered. Thus, for QSAR methods, which represent a major group
of the in silico methods (other in silico methods are the docking methods, which
are important for pharmaceutical industry and drug discovery, and will not be
addressed here), it is important to underline that, according to legislation, the
scientific validity is the key factor, and not a formal process of validation.
According to REACH by now QSAR methods are applicable to the following
tasks: to fulfill information requirements (use of predictions instead of test data),
as part of the weight of evidence approach, to support category justification (use to
justify structural and metabolic similarities) and for integrated testing strategies.
Thus, we will adhere to this position. However several publications show the
effective capacity of QSARs in the prediction of different endpoints, such as
carcinogenicity [16].
The recent position of the USA is to take into consideration the scientific validity
of the tool, and not necessarily the validation process. This is the philosophy
adopted within the Tox21 (http://epa.gov/ncct/Tox21/) and ToxCast (http://www.
epa.gov/ncct/toxcast/) initiatives. The reason for this is that the validation process
takes 10 years or more before a method is officially approved, and this period would
seriously limit the possibility to rapidly produce the necessary data needed within
few years. Furthermore, the techniques are rapidly changing.
88 N.G. Bakhtyari et al.

What we describe here is not necessarily the result of a formal validation
process, but conversely we preferred to provide a list which is scientifically updated
and may offer advanced, modern tools useful for stakeholders. However, for in vitro
methods, the formal validation process should be followed.
A second important consideration refers to the applicability of these two
different categories of approaches. QSAR methods have to be applied to individual
chemicals. The QSAR approach can be profitably used coupled to a chemical
analysis, exploiting the information on the contaminant occurrence. However, if
the user wants to address a mixture of chemicals, the components of the mixture
have to be addressed separately and individually. In case of unknown compounds,
QSAR cannot be used.

3 Conclusions

It is expected that the alternative methods are going to be more and more used. The
overall prospective is that these methods will offer possibilities addressing toxicity on
a different angle compared to classical methods. Thus, they can also be integrated
within a weight of evidence approach.

References

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9. Ekins S (2007) Computational chemistry: risk assessment for pharmaceutical and environ-
mental chemicals. Wiley, Hoboken, New Jersey
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document/2/0,3746,en_2649_34379_42926338_1_1_1_1,00.html
11. Helma C (2005) In silico predictive toxicology: the state-of-the-art and strategies to predict
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13. Enoch SJ, Cronin MTD, Madden JC, Hewitt M (2009) Formation of structural categories to
allow for read-across for teratogenicity. QSAR Comb Sci 28(6–7):696–708
14. Hewitt M, Ellison CM, Enoch SJ, Madden JC, Cronin MTD (2010) Integrating (Q)SAR
models, expert systems and read-across approaches for the prediction of developmental
toxicity. Reprod Toxicol 30(1):147–160
15. Worth AP, Balls M (eds) (2002) Alternative (non-animal) methods for chemicals testing:
current status and future prospects. A report prepared by ECVAM and the ECVAM working
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16. Milan C, Schifanella O, Roncaglioni A, Benfenati E (2011) Comparison and possible use of in
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A Revision of Current Models for Environmental
and Human Health Impact and Risk Assessment
for Application to Emerging Chemicals

J. Rovira, M. Nadal, J.L. Domingo, T. Tanaku, N.A. Suciu, M. Trevisan,
E. Capri, X. Seguı́, R.M. Darbra, and M. Schuhmacher

Abstract Nowadays, we are living in the global circular economy, where products
are produced, used, and finally disposed in different parts of the world. These
products have a huge amount of additives, that in many cases can be hazardous if
they are not treated properly. The risk assessment of human health and the environ-
ment due to exposure to chemical additives is necessary.
In this chapter the risk assessment is briefly introduced. Risk assessment is
divided into four steps: hazard identification, hazard characterization, exposure
assessment, and risk characterization. This chapter also highlights five risk and
life cycle impact assessment models (EUSES, USEtox, GLOBOX, SADA, and
MAFRAM) that allows for assessment of risks to human health and the environ-
ment. In addition other 12 models were appointed. Finally, in the last section of this
chapter, there is a compilation of useful data sources for risk assessment. The data
source selection is essential to obtain high quality data. This source selection is
divided into two parts. First, six frequently used databases for physicochemical

J. Rovira (*) and M. Schuhmacher
Environmental Analysis and Management Group, Departament d’Enginyeria Quı́mica, Universitat
Rovira i Virgili, Av. Paı̈sos Catalans 26, 43007 Tarragona, Spain
Laboratory of Toxicology and Environmental Health, School of Medicine, IISPV, Universitat
Rovira i Virgili, San Llorenç 21, 43201 Reus, Spain
e-mail: joaquim.rovira@urv.cat
M. Nadal and J.L. Domingo
Laboratory of Toxicology and Environmental Health, School of Medicine, IISPV, Universitat
Rovira i Virgili, San Llorenç 21, 43201 Reus, Spain
T. Tanaku, N.A. Suciu, M. Trevisan, and E. Capri
Institute of Agricultural and Environmental Chemistry, Università Cattolica del Sacro Cuore,
Via Emilia Parmense 84, 29100 Piacenza, Italy
X. Seguı́ and R.M. Darbra
Department of Chemical Engineering, Universitat Politècnica de Catalunya, Diagonal 647, 08028
Barcelona, Spain

B. Bilitewski et al. (eds.), Global Risk-Based Management of Chemical Additives II: 91
Risk-Based Assessment and Management Strategies, Hdb Env Chem (2013) 23: 91–108,
DOI 10.1007/698_2012_171, # Springer-Verlag Berlin Heidelberg 2012,
Published online: 10 July 2012
92 J. Rovira et al.

and/or toxicological properties (TOXNET, eChemPortal, ATDSR, CPDB,
IUCLID, and ECOTOX) are presented. Second, six estimation data tools are
pointed. The estimation tools are useful when it is not possible to find data
parameters to assess the risk, for example, in the case of emerging pollutants or
new substances.
In conclusion, there is no risk assessment model better than another. All models
have their strengths and weaknesses. Many of them are focused on one particular
aspect such as a single environmental compartment or in a kind of pollutant. It is
important to remark that the selection of the data source is essential to obtain quality
results.

Keywords Environmental and risk assessment models, Life-cycle Impact assess-
ment models, Physicochemical and toxicological database

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
2 Risk Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
3 Human Health Risk Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3.1 Hazard Identification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3.2 Hazard Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3.3 Exposure Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
3.4 Risk Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4 Environmental Risk Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
5 Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
5.1 European Union System for the Evaluation of Substances . . . . . . . . . . . . . . . . . . . . . . . . . 99
5.2 USEtox™ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
5.3 GLOBOX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
5.4 Spatial Analysis and Decision Assistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
5.5 Multimedia Agricultural Fate and Risk Assessment Model . . . . . . . . . . . . . . . . . . . . . . . . 102
5.6 Other Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
6 Data Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
6.1 Data Bases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
6.2 Estimation Data Tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
7 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106

1 Introduction

Currently, in the global economy, products are manufactured in one part of the
world, used in another part and there is little knowledge about where these products
will be disposed of. Most consumer products contain a large variety of chemical
additives, in many cases, new substances, since they are poorly studied. This
together with the lack of knowledge about the additives used, cause concern
about the impact of these additives on human health and the environment.
These additives may come into contact with humans and the environment not
only during the use of the product but also through their life cycle: during the
A Revision of Current Models for Environmental and Human Health Impact and. . . 93

Fig. 1 Risk analysis structure
(adapted from FAO [2])

production of the additive, during the manufacture of consumer product where the
additives are used, and during the product’s end of life treatment. As discussed in
the previous chapter (see [4]), the emissions of the additives in a given environ-
mental compartment are distributed to others. Therefore, the human population is
not only exposed directly to these additives by the use of products but also
indirectly through the environment. Moreover, these substances can also enter
into the food chain and accumulate in fish, animals, crops, fruits, and vegetables
where they could later be ingested by humans.
Due to this, it is necessary to assess the risk to human health and the environment
due to the exposure to these chemical additives. In this chapter the impacts that a
substance can cause to a certain receptor (humans and the environment) and the
harms to the receptor at different exposure levels are identified in hazard identifi-
cation and hazard characterization steps, respectively. Exposure assessment takes
into account the amount, frequency, and duration of the exposure to the substance.
Finally, risk characterization evaluates the increased risk caused by such exposure
to the exposed population.
This chapter also highlights a selected number of models that allow for assess-
ment of risks to human health and the environment. Finally, in the last section of
this chapter, there is a compilation of useful data sources for risk assessment.

2 Risk Assessment

Risk analysis is defined as a process for controlling situations where a target could
be exposed to a hazard [1]. It consists of three parts: risk assessment, risk manage-
ment, and risk communication (Fig. 1). Risk communication is the exchange of
information about risks between risk assessors, public managers, policy makers,
interested groups, and the general population. Risk management is related to
decision-making processes involving considerations of political, social, economic,
and technical factors with relevant risk assessment information.
The organization for economic co-operation and development (OECD) defines
risk assessment as the process intended to calculate or estimate the probability,
including the identification of attendant uncertainties, of an adverse effect in an
94 J. Rovira et al.

organism, system, or (sub) population caused under specified circumstances by
exposure to an agent, taking into account the inherent characteristics of the agent of
concern as well as the characteristics of the specific target system [1]. According to
this definition the risk assessment process consists of four steps:
1. Hazard identification consists in identifying the type and nature of adverse
effects caused by the agent in the receptor (target organism, system, or (sub)
population).
2. Hazard characterization (or dose–response assessment) is the qualitative and, as
far as possible, quantitative description of the inherent properties of an agent or
situation having the potential to cause adverse effects. This step should include
a dose–response assessment that describes the severity of adverse effects
(the responses) related to the amount and condition of exposure to an agent
(the dose).
3. Exposure assessment is the process of predicting or estimating the concentration
or amount of an agent, the frequency, and the duration that reaches the receptor.
4. Risk characterization is the determination, qualitative and as far as possible
quantitative, of the probability of occurrence of adverse effects in a given target,
under the predicted or estimated exposure conditions.
In the following two sections, a deeper explanation of human health and
environmental risk assessment is given.

3 Human Health Risk Assessment

3.1 Hazard Identification

The goal of the hazard identification is to identify the effects of substance to
environment or human health.
A substance can cause one or more effects. Common effects are acute and long-
term toxicity, skin irritation, corrosiveness, sensitization, mutagenicity, carcinoge-
nicity, reproductive effects, and developmental toxicity.

3.2 Hazard Characterization

Hazard characterization is the estimation of the relationship between the dose of a
substance and the effects observed. To evaluate this relationship, the following
studies can be performed (in order of reliability):
– Human studies including case reports, epidemiological studies, and, in some
cases, direct human studies (with volunteers). The advantages of these studies
are that toxic effects are evaluated in humans and no interspecies extrapolation is
A Revision of Current Models for Environmental and Human Health Impact and. . . 95

needed. However, the subjects of these studies are exposed to an uncontrolled
environment that may interfere with the results.
– Animal toxicological and in vitro studies. In animal or in vitro studies the system
is more controlled than in human studies, the external influences are minimized
(more in in vitro than in animal tests). However, in both cases, an extrapolation is
required: interspecies in the case of animal studies and at least from system to
organism extrapolation in the case of in vitro test.
– Qualitative structure–activity relationship (QSAR) methods (see Sect. 5.2).
For the two aforementioned steps, hazard identification and hazard characteriza-
tion, data adequacy is of high importance. The data adequacy is defined by the
reliability and the relevance of the data for human risk assessment [3].

3.3 Exposure Assessment

Exposure assessment is one of the most important steps in risk assessment. It is the
process that predicts or estimates the amount of the substance under study that
reaches the human body. To assess the exposure, it is necessary to define in detail
the exposure pathway, the route of exposure, the concentration of the pollutant in
the particular media, the contact rate, the frequency of exposure, and the population
exposed (age, gender, and vulnerable population, among others). A general equa-
tion (Eq. 1) to determine the exposure dose is as follows:

Concentration  Contact Rate  Frequency
Dose  (1)
Body weight

3.3.1 Exposure Routes

Exposure pathway describes how the substances enter into the human body. All
possible pathways are not considered for all substances and emission scenarios,
only the ones that are relevant for a specific substance and emission scenario are
included. For example in the case of substances that are not present in the air, the
inhalation route is not taken into account.
The most common routes of exposure are:
– Inhalation, of air and particles.
– Ingestion, of soil, dust, food, and drinking water.
– Dermal contact: absorption through the skin.
– Other common routes of exposition could be percutaneous, in the case that the
substance enters into the body through a wound in the skin, or intravenous in the
case of direct injection into the bloodstream.
96 J. Rovira et al.

3.3.2 The Need of Realistic Scenarios for Exposure Evaluation

For human health risk assessment, it is necessary to elaborate realistic scenarios.
Knowledge of real scenarios where the contaminant is emitted to the environment
will help to obtain information about the fate and transport of the contaminant once
emitted to the environment and the route of exposure for the human beings living in
this scenario of concern. There are different types of exposure, i.e., direct, indirect
(as is the case of food contaminated by the air, water, or soil contaminated by the
emission), occupational exposure, and consumer goods coming from outside the
scenario of concern. Depending on the objective of the study, it will be necessary to
consider in the exposure assessment one or more types of exposure.
In each context, it is essential to define suitable parameters of the exposure
scenario for a realistic risk assessment:
– Environmental exposure (direct). Exposure through air inhalation, soil and dust
ingestion, and dermal contact of soil and dust are the principal exposure
pathways. Other exposure pathways (e.g., water dermal contact) can be taken
into account in some scenarios. Monitoring campaigns or multimedia fate
models are used to assess the exposure (see [4]).
– Food and water ingestion (dietary exposition). To assess the dietary exposure,
ingestion rates of the different food products and water are needed. Multimedia
fate models or food sampling campaigns are the main ways to determine the
concentration of substances in food products and water at the specific scenario.
These models consider cattle, meat, milk, fish, crops, and drinking water, among
others.
– Occupational exposure (work place exposure). Exposure may occur as a singular
event, a repetition singular event, or as continuous exposure during the work
time. Exposure can be through inhalation, ingestion, or dermal contact. Every
workplace has its characteristics, therefore information have to be collected
about the substances, duration of exposure, and frequencies of exposure,
among others. One aspect to be considered in the exposure assessment at work
is whether or not workers are using personal protective equipment. Exposure
models and monitoring of contaminants in the workplace are the two most
widely used tools for exposure assessment. Biological monitoring (e.g.. blood,
hair, breast milk) of the workers can give additional information on the occupa-
tional exposure to a substance.
– Consumer goods (nondietary). The consumer is a member of the general popu-
lation, who may be exposed to (a new or existing) substance by using consumer
products. The examples are almost endless, exposure to solvents used in
adhesives, paints, and furniture, substances that can be released from a consumer
product, the exposure to substances used for cleaning and decoration of houses,
exposure to raw materials of cosmetics, etc. The wide range of cases makes it
impossible to generalize a scenario. Substance data quality (amount in products,
exposure pathway) and the consumer goods (frequency and duration of use,
users of that product) are essential to build a realistic exposure scenario.
A Revision of Current Models for Environmental and Human Health Impact and. . . 97

3.4 Risk Characterization

The last step in risk assessment is the risk characterization where the probability
and the severity of adverse health effects in the exposed population are assessed.

3.4.1 Noncarcinogenic Risk

In the case of noncarcinogenic substances, there exists a threshold; this is an
exposure with a dose below which there would not be adverse effect on the
population that is exposed. This is the reference dose (RfD), and it is defined as
the daily exposure of a human population without appreciable effects during a
lifetime. The RfD value is calculated by dividing the no observed effect level
(NOEL) by uncertainty factors. When NOEL is unknown, the lowest observed
effect level (LOEL) is used. NOEL and LOEL are usually obtained in animal
studies. The main uncertainty factor, usually tenfold, used to calculate the RfD
are the following: the variations in interspecies (from animal test to human),
presence of sensitive individuals (child and old people), extrapolation from
subchronic to chronic, and the use of LOEL instead of NOEL. Noncancer risk is
assessed through the comparison of the dose exposed calculated in the exposure
assessment and the RfD. The quotient between both, called in some studies as
hazard quotient, is commonly calculated (Eq. 2). According to this equation,
population with quotient >1 will be at risk to develop some specific effect related
to the contaminant of concern.
Dose
Risknoncancer ¼ : (2)
RfD

3.4.2 Carcinogenic Risk

There is some controversy regarding the carcinogenic effects [5]. There exist two
main points of view that define the carcinogenic risk characterization. The first one
considers that there is no threshold dose in the carcinogenic substances due to
exposure at any level of the substance that may have a probability to cause adverse
effects (tumoral cell) [5]. The second point of view suggests that the human body
can detoxify a carcinogenic substance in low doses and in consequence, a threshold
exists for that carcinogenic substance. To protect the human health, the
no-threshold approach is commonly chosen. Different mathematical models are
used (linear in low dose model, nonlinear models, and multiextrapolation models).
In the low-dose region, the equation (Eq. 3) is used to assess the risk, where SF is
the slope factor, a toxicity value for evaluating the probability of an individual
developing cancer from exposure to contaminant levels over a lifetime:

Riskcancer ¼ Dose  SF: (3)
98 J. Rovira et al.

4 Environmental Risk Assessment

The hazard identification and hazard characterization steps that some
methodologies define as a single step as “Effect assessment,” estimate the predicted
no effect concentration (PNEC) in each environmental compartment. PNEC, that
means the concentration below which an adverse effect will most likely not occur,
is usually calculated on the basis of results of laboratory monospecies test. The
PNEC is calculated by dividing the lowest value of toxicity test L(E)C50 (short
term) or no observed effect concentration (NOEC) (long term) by an assessment
factor. The assessment factor represents the uncertainty in: the variability in intra-
and interspecies, the short to long toxicity extrapolation, and the extrapolation of
the laboratory toxicity test for a limited number of species to a real environment.
The assessment factor depends on the number of species tested and the trophic
levels selected, the quality of data, and the duration of the test (short or long term).
For example, in the European Commission Technical Guidance Document on Risk
Assessment [3], an assessment factor of 1,000 is used to calculate aquatic PNEC if a
minimum of one short term L(E)C50 for each of the three trophic levels is known.
On the other hand, an assessment factor of 10 is used if long-term NOECs are
known for at least three species representing the three trophic levels.
Exposure assessment using monitoring data or fate and transport models calcu-
late the predicted environmental concentration (PEC) in each environmental com-
partment. More information can be obtained from Suciu et al. [4].
Finally, in the risk characterization step, the PEC/PNEC quotient that defines the
risk of the substance in the environment is calculated. If the quotient (PEC/PNEC)
is less than 1, the substance do not present risk to the environment. More informa-
tion is available in the European Commission “Technical Guidance Document on
Risk Assessment” [3] and in the United States Environmental Protection Agency’s
“Guidelines for Ecological Risk Assessment” [6].

5 Models

There are many models for assessing risks to human health and/or the environment.
Some of them are multimedia models, which assess the exposure and risks in
different environmental matrices, such as soil, air, water, and food chains with
different degrees of complexity within each medium. Conversely, others are more
specific with regard to a medium or a system (e.g., river or food chain). Other
models assess only human health risks or environmental risks, while some assess
both risks. Based on the type of scenario that is studied, an appropriate model will
be chosen.
A Revision of Current Models for Environmental and Human Health Impact and. . . 99

Table 1 Differences in the principles of assessing the potential for ecotoxicological and toxico-
logical effects in risk assessment vs. life cycle impact assessment (based on Olsen et al. [7])
Risk assessment (RA) Life cycle impact assessment (LCIA)
Absolute assessment Relative assessment due to the use of a
functional unit
Chemical-oriented Product-oriented
For specific circumstances of use or For products during their entire life cycles
environmental recipients
Typically carried out by or for the authorities Its use is controlled primarily by the needs of the
companies
The result expresses a verifiable risk of effect The result is a relative environmental impact
potential that cannot be verified
Tiered approach; a conservative assessment of, A conservative assessment is unwanted; a true
particularly, the exposure can be used in the measure of the environmental impact is
preliminary steps aimed

Apart from the risk assessment models, there exist models for assessing impacts
to human health and the environment in LCA. Both tools [risk assessment and life
cycle impact assessment (LCIA)] have different purposes and aims that are
summarized in Table 1 [7].
Despite the fact that there exist some differences between both methodologies,
the cooperation between the aforementioned tools seems to be advantageous to use
in environmental management [7]. Moreover, there are also steps in LCIA that also
exist in the risk assessment (i.e., exposure assessment). Therefore, models used in
LCIA can be used also to assess human or environmental exposure to chemicals.
For that reason LCIA models are also included in the review of models of risk
assessment.
Following, a brief summary of selected models currently used is showed.

5.1 European Union System for the Evaluation of Substances

The European Union System for the Evaluation of Substances (EUSES) [8] is the
software provided by European Chemical Bureau (ECB) to implement the EU
Technical Guidance Documents on Risk Assessment for new notified substances,
existing substances, and biocides [3]. The development of EUSES 2.1 was
commissioned by the European Commission to the National Institute of Public
Health and the Environment (RIVM) of the Netherlands. The work was supervised
by an EU working group comprised of representatives of the JRC-European
Chemicals Bureau, EU Member States, and the European chemical industry.
100 J. Rovira et al.

The EUSES environment is represented as a set of nested scales. The local scale
is nested into the regional scale which is nested in the continental scale. The
continental scale is nested into the moderate climate zone, which has two adjacent
zones, an arctic and a tropic zone, respectively. All the scales are divided into boxes
(environmental compartments). The boxes of all scales include at least air, soil,
water, and sediment compartments.
The human and environmental protection goals in EUSES are: human
populations (workers, consumers, and man exposed via the environment) and
ecological systems (micro-organisms in sewage treatment systems, aquatic
ecosystems, terrestrial ecosystems, sediment ecosystems, and predators). Repeated
dose toxicity, fertility toxicity, maternal toxicity, developmental toxicity, carcino-
genic risk, and lifetime cancer risk can be calculated for the cases that literature data
is available.
The risk characterization procedure will result in a quantitative comparison per
substance of the outcome of the exposure assessment and of the effects assessment.
This comparison is made through the ratio PEC/PNEC. The generic name for PEC/
PNEC in EUSES is risk characterization ratio (RCR). Other ratios are used in
EUSES for the risk characterization such as the margin of safety (MOS) or the ratio
of the estimated no-effect or effect level parameter to the estimated exposure level
for human subpopulations and the acceptable operator exposure level (AOEL).
The exposure assessment in EUSES aims at “reasonable worst-case,” i.e., the
exposure scenario was the worst scenario without being unrealistic and as much as
possible using mean, median, or typical parameter values. If the outcome of the
“reasonable worst-case” risk characterization indicates that the substance is “not of
concern,” the risk assessment for that substance can be stopped with regard to the
scenario considered.

5.2 USEtox™

In 2005, a comprehensive comparison of LCIA toxicity characterization models
was initiated by the United Nations Environment Program (UNEP) and the Society
for Environmental Toxicology and Chemistry (SETAC) in their life cycle initiative.
The main objectives of this effort were to [9] (1) identify specific sources of
differences between the models’ results and structure; (2) detect the indispensable
model components; and (3) build a scientific consensus model from them,
representing recommended practice.
An extensive comparison of the most obvious positive and negative aspects from
seven evaluation models (ECOSENSE, EDIP, USES-LCA, CalTOX, BETR,
IMPACT 2002+, and WATSON) led to the development of USEtox, a scientific
consensus environmental model for characterization of human and ecotoxicological
A Revision of Current Models for Environmental and Human Health Impact and. . . 101

impacts in LCIA that contains only the most influential model elements. USEtox
was developed following a set of principles, including [9]:
• Parsimony: as simple as possible, as complex as necessary.
• Mimetic: not differing more from the original models than these differ among
themselves.
• Evaluated: providing a repository of knowledge through evaluation against a
broad set of existing models.
• Transparent: being well-documented, including the reasoning for model choices.
USEtox calculates characterization factors for human toxicity and freshwater
ecotoxicity. Assessing the toxicological effects of a chemical emitted into the
environment implies a cause–effect chain that links emissions to impacts through
three steps: environmental fate, exposure, and effects. Linking these steps, a
systematic framework for toxic impacts modeling based on matrix algebra was
developed to some extent within the OMNIITOX project [10]. USEtox covers two
spatial scales, the continental and the global scales.
According to the creators, USEtox provides a parsimonious and transparent
tool for human health and ecosystem characterization factor (CF) estimates. It has
been carefully constructed as well as evaluated via comparison with other models
and falls within the range of their results while being less complex.

5.3 GLOBOX

GLOBOX [11] is a spatially differentiated multimedia fate, exposure, and effect
model. It is used for the calculation of spatially differentiated LCA characterization
factors on a global scale. It can also be used for human and environmental risk
assessment. The GLOBOX is based on the EUSES 2.0 model. It has primarily been
constructed for the calculation of spatially differentiated LCA characterization
factors on a global scale. In comparison with the EUSES model, the GLOBOX
has a higher level of spatial differentiation, in such a way that the GLOBOX is
spatially differentiated with respect to fate and human intake on the level of
separated but interconnected countries and oceans/seas. The main goal of the
GLOBOX is to construct location-specific characterization factors for any
emissions at any locations over the world, considering summed impacts of such
emissions in different countries and seas/oceans. The GLOBOX model consists of
the following three main modules: an impact-category independent fate module, a
human-intake module, and an effect module.
Twelve distribution compartments are distinguished: air, rivers, freshwater
lakes, freshwater lake sediments, salt lakes, salt lake sediments, natural, agricul-
tural and urban soil, groundwater, sea water, and sea water sediments. In contrast
102 J. Rovira et al.

to the EUSES model, where different nested scales (one inside the other) are
considered, the GLOBOX is a system of interconnected regions at the same level
in the model.

5.4 Spatial Analysis and Decision Assistance

Spatial Analysis and Decision Assistance (SADA) [12] is a free software, devel-
oped at the Institute for Environmental Modelling at the University of Tennessee.
SADA incorporates tools from environmental assessment fields into an effective
problem-solving software. These tools include integrated modules for human health
risk assessment and ecological risk assessment and also geographical information
system (GIS), visualization, geospatial analysis, statistical analysis, cost/benefit
analysis, sampling design, and decision analysis.
SADA provides a full human health risk assessment module and associated
databases. The risk models follow the USEPA’s Risk Assessment Guidance for
Superfund (RAGS) and can be customized to fit site-specific exposure conditions. It
calculates risks based on the following exposure pathways: ingestion, inhalation,
dermal contact, food consumption, and also a combined exposure.
The ecological risk module allows users to perform benchmark screenings for
surface water, sediment, soil, and biota. Accompanying the ecological risk module
is a database of benchmarks and other information that are supported and updated
on the SADA web site. Benchmarks are adjusted for site-specific physical
parameters as appropriate.

5.5 Multimedia Agricultural Fate and Risk Assessment Model

Multimedia Agricultural Fate and Risk Assessment Model (MAFRAM) [13] is a
comparing and ranking method for new and existing nonvolatile organic
compounds (NVOCs) used in agricultural activities. MAFRAM was intended to
compare and establish the general features of NVOCs behavior and assess the
ecotoxicological risk to the ecosystem.
MAFRAM divides the agricultural environment into two main zones, which are
the on- and off-farm zones. Six compartments (air, water, soil, sediment, above-
ground plants, and roots) are included in on- and off-farm zones. The MAFRAM
output includes the intercompartmental transport and transfer rates, the primary loss
mechanisms, chemical concentration, amount, residence time, and the rank of risk
in each compartment.
A Revision of Current Models for Environmental and Human Health Impact and. . . 103

Table 2 Models used in human health and/or environmental risk assessment
Model Description Ref
BREEZE® Risk Human health and ecological risk assessment modeling system designed [14]
Analyst to conduct multipathway human health risk assessments and food-
web based ecological risk assessment modeling. BREEZE risk
analyst combines databases, GIS functionality, fate, transport, and
exposure modeling equations into one software application
IRAP-h View™ Interface for conducting a comprehensive multipathway human health [16]
risk assessment. It simultaneously calculates risk values for multiple
chemicals, from multiple sources, at multiple exposure locations.
IRAP-h view implements the US EPA – OSW Human Health Risk
Assessment Protocol (HHRAP) US EPA [15]
Eco Risk View™ An advanced ecological risk assessment program for conducting a [16]
comprehensive multipathway ecological risk assessment by
simultaneously calculating risk values for multiple chemicals, from
multiple sources, at multiple exposure locations. EcoRisk view fully
implements US EPA guidance for evaluating ecological risks [17]
EcoFate EcoFate is a software package for conducting ecosystem based [18]
environmental and ecological risk assessments of chemical
emissions by point and non-point sources in freshwater and marine
aquatic ecosystems, including lakes, rivers and marine inlets
RISC5 RISC5 is a software package for performing fate and transport modeling, [19]
human health risk assessments and ecological risk assessments for
contaminated sites. Fate and transport models are available in RISC5
to estimate receptor point concentrations in groundwater and indoor
and outdoor air. It can be used to estimate the potential for adverse
human health impacts (both carcinogenic and noncarcinogenic) from
up to nine exposure pathways
Ecolego Ecolego is a powerful and flexible software tool for creating dynamic [20]
models and performing deterministic or probabilistic simulations.
Ecolego can be used for conducting risk assessments of complex
dynamic systems evolving over time with any number of species.
Ecolego has specialized databases and other add-ons designed for the
field of radiological risk assessment
@RISK @RISK performs risk analysis using Monte Carlo simulation to conduct [21]
sensitivity and uncertainty analyses
API-DSS Exposure and Risk Assessment Decision Support System Software. [22]
Estimates human exposure and risk from sites contaminated with
petroleum products
XtraFood Xenobiotics transfer in the primary FOOD Chain model calculates [23]
transfer of contaminants in the primary food chain. This model
describes the whole chain from immission of contaminants at the
farm level over concentrations in food to human exposure. The
model focuses on the terrestrial food chain
RISKAT RISKAT assesses the risks to populations in the vicinity of plants [24]
processing and storing toxic and flammable materials
CHARM CHARM is used to carry out environmental risk assessments of [25]
discharges of exploration and production of chemicals, from
platforms into the marine environment
Impact 2002 This model provides close to 1,000 characterization factors for the [26]
midpoint categories human toxicity, aquatic ecotoxicity, and
terrestrial ecotoxicity according to the LCIA methodology. The
model is parameterized in a nonspatial and a spatial European model
nested in a nonspatial world model, as well as a complete world
model
104 J. Rovira et al.

5.6 Other Models

In addition to the models presented above, there are a number of other risk
assessment models available. Table 2 briefly presents some of these models that
can be used to assess the risk of human health and the environment.

6 Data Sources

In order to run these models, it is necessary to have input data, mainly physico-
chemical properties and toxicological data (for both human and ecosystems), which
can be extracted from different information sources. The source selection is essen-
tial to obtain data of high quality. In some cases (e.g., emerging pollutants) there is a
lack of physicochemical and toxicological data which makes it necessary to use
tools such as QSARs.

6.1 Data Bases

Currently, there are many databases where the physicochemical, toxicological
parameters required to perform a risk assessment can be obtained. It must be
borne in mind that the existence of a quality control parameters included in the
databases is of great importance. This quality control can be accomplished through
periodic updating of the database, the inclusion of bibliographical references of the
origin of each parameter, peer reviewed bibliography, etc.
In Table 3, a selection of physicochemical and toxicological databases is shown.
These databases are selected according to the existence of quality controls and their
free online availability.

6.2 Estimation Data Tools

Despite the existence of several databases for certain substances, it is not possible to
find physicochemical and/or toxicological parameters to assess the risk for all
substances. The lack of data is one of the main problems in risk assessment. This
is especially true for emerging pollutants. One solution to solve this problem is the
use of QSAR or estimation tools. QSAR models correlate the structure of the
substance with their activities (physicochemical properties, environmental fate,
and/or toxicological properties).
A Revision of Current Models for Environmental and Human Health Impact and. . . 105

Table 3 Physicochemical and toxicological databases
Database Description
TOXNET The Toxicology Data Network is a cluster of databases covering toxicology,
hazardous chemicals, environmental health, and related areas published by the
United States Library of Medicine. The TOXNET includes, among others,
toxicological databases such as Chemical Carcinogenesis Research Information
System (CCRIS), Hazardous Substances Data Bank (HSDB), Integrated Risk
Information System (IRIS), International Toxicity Estimates for Risk (ITER),
and ChemIDplus
eChemPortal eChemPortal is a global portal for information regarding chemical substances. It
allows simultaneous searching of reports and datasets by chemical name, CAS
number, or by chemical property. Direct links to collections of chemical hazard
and risk information prepared for government chemical review programs at
national, regional, and international levels are obtained. Classification results
according to national/regional hazard classification schemes or to the Globally
Harmonized System of Classification and Labeling of Chemicals (GHS) are
provided when available
ATDSR The Agency for Toxic Substances and Disease Registry produces the “toxic
substances profile” for hazardous substances found in National Priority List
(NPL) sites. These hazardous substances are ranked based on the frequency of
occurrence at NPL sites, toxicity, and potential for human exposure
CPDB The Carcinogenic Potency Database contains the results of 6,540 chronic, long-
term animal cancer tests on 1,547 chemicals. The CPDB provides easy access to
the bioassay literature, with qualitative and quantitative analyses of both
positive and negative experiments that have been published over the past
50 years in the general literature through 2001 and by the National Cancer
Institute/National Toxicology Program through 2004
IUCLID The International Uniform Chemical Information Database is a software
application to capture, store, maintain, and exchange data on intrinsic and
hazard properties of chemical substances
ECOTOX The ECOTOX is a database of single chemical toxicity data for aquatic life,
terrestrial plants, and wildlife

A selection of the most relevant physicochemical and toxicological estimation
tools, which are freely available, are presented below in Table 4.

7 Conclusions

In this chapter human health and environmental risk assessment steps were
introduced. Five models (EUSES, USEtox, GLOBOX, SADA, and MAFRAM)
risk and LCIA models were briefly described and also other 12 models were
appointed. There is no risk assessment model better than another. All models
have their strengths and weaknesses and many of them also are focused on one
106 J. Rovira et al.

Table 4 Most relevant QSAR tools to estimate physicochemical and toxicological properties
Tool Description Ref
EPI Suite v4.0 EPIsuite estimate among other Kow, Koc, Koa, Henry’s Law constant, [27]
melting and boiling points, aerobic and anaerobic biodegradability
of organic chemicals, biodegradation of half-life of hydrocarbons,
and bioconcentration factors
Danish (Q)SAR The Danish (Q)SAR database is a repository of estimates from over 70 [28]
Database (Q)SAR models for 166,072 chemicals. The (Q)SAR models
encompass endpoints for physicochemical properties, fate,
ecotoxicity, absorption, metabolism, and toxicity
TEST TEST allows for estimates of the value for several toxicity endpoints: [29]
96 h Fathead minnow LC50, 48 h Daphnia magna LC50, 48 h
Tetrahymena pyriformis IGC50, Oral rat LD50, bioaccumulation
factor, developmental toxicity, and Ames mutagenicity. TEST also
estimates several physical properties
CAESAR Five endpoints with high relevance for REACH have been addressed [30]
within CAESAR: bioconcentration factor, skin sensitization,
carcinogenicity, mutagenicity, and developmental toxicity
ECOSAR Chemical’s acute (short term) toxicity and chronic (long term or [31]
delayed) toxicity to aquatic organisms, aquatic invertebrates, and
aquatic plants are estimated
OECD QSAR It is developed by OECD to make (Q)SAR technology readily [32]
Toolbox accessible, transparent, and less demanding in terms of
infrastructure costs. The toolbox has multiple functionalities
allowing the user to perform a number of operations. The toolbox
potentially covers all relevant regulatory endpoints

particular aspect such as a single environmental compartment or focused in a kind
of pollutants. Finally, freely and on line available data sources (databases and
estimation data tools) were reviewed. The selection of the data source and, in
some cases the scarcity of data are an important issue to obtain quality results.

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Larsen HF, MacLeod M, Margni M, McKone TE, Payet J, Schuhmacher M, van de Meent D,
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Office of Solid Waste. Washington, DC
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2012
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Assessment Protocol (SLERAP) for Hazardous Waste Combustion Facilities EPA 530-D-
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contaminants in primary food products. Study report of the Belgian Science Policy. Brusels,
Belgium
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Methodology. Report No HSL/2002/Z27. Sheffield, UK
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Accessed 09 Mar 2012
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A Program to Estimate Toxicity from Molecular Structure United States Environmental
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Chem Cent J 4:I1
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Are Chemicals in Products Good or Bad
for the Society? – An Economic Perspective

Stefan Åstr€
om, Maria Lindblad, Jenny Westerdahl, and Tomas Rydberg

Abstract Humans have introduced a large number of chemical substances into
products over the past century. We use the chemicals since they provide utility for
the product itself, and thereby for the society. However, since many chemicals are
toxic and harmful for both the environment and human health, and as they are
emitted from the products during its lifecycle, the social benefits of using them
are reduced. According to standard economic theory, the value of the product is
equal to its price. However, in most cases the full cost of a product is rarely shown
in the price of the product. Even though the product is being purchased by an
individual or a company, the impact of the product will affect other than the buyer
of the product. There are also unknown impacts that can affect both the buyer and
the producer of the product or a third party. These impacts are in economic
terminology often summarized as “externalities” (external impacts). External
impacts might be negative or positive. Also, they can come in many different
shapes. They are external because the affected party does not receive any compen-
sation and the polluter does not need to pay without being obliged. This chapter
gives a fast version of environmental economics needed for understanding of the
topic and discusses different socio-economic aspects related to chemicals in
products with the aim to give an overview of the subject.

Keywords Environmental economics, Cost-benefit analysis, Chemical additives

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
2 Background Economic Theory Related to External Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
2.1 The Buyer: Homo Economicus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111

S. Åstr€om (*), M. Lindblad, J. Westerdahl, and T. Rydberg
IVL Swedish Environmental Research Institute, P.O. Box 53021, 400 14 G€
oteborg, Sweden
e-mail: stefan.astrom@ivl.se

B. Bilitewski et al. (eds.), Global Risk-Based Management of Chemical Additives II: 109
Risk-Based Assessment and Management Strategies, Hdb Env Chem (2013) 23: 109–136,
DOI 10.1007/698_2012_184, # Springer-Verlag Berlin Heidelberg 2012,
Published online: 23 August 2012
110 S. Åstr€
om et al.

2.2 The Seller . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
2.3 The Market . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
3 Externalities and External Costs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
3.1 Externalities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
3.2 External Costs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
3.3 Theories for Avoiding Welfare Losses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4 Valuating Externalities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
4.1 Economic Values at Stake . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
4.2 Methods to Valuing Externalities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
5 Limitations with Economic Valuation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
5.1 Valuation Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
5.2 General Concerns Related to Economics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
6 Identification of Impacts and Their Stressors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
6.1 Impacts on Human Health and the Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
6.2 Economic Impacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
7 Economic Tools for Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
7.1 Cost–Benefit Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
7.2 Impact Pathway Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
7.3 EPS Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
8 Examples of Valuation of Impacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
8.1 Economic Valuation of Lead Emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
8.2 Example of Economic Valuation Results Linked to Environmental
and Health End Points . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
8.3 Illustrative Cost–Benefit Analysis of Flame Retardants in Furniture . . . . . . . . . . . . . . 131
9 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
10 Buzz Words . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134

1 Introduction

Studies in environmental economics and economic valuation often produce results
that can appear slightly difficult to accept for the layman (and experts).
As examples, economists have calculated the welfare loss induced by a premature
death to some ~€1 million (central estimate) [1, 2]. The welfare loss caused by
a mild cough is estimated to some €38 [2], and the loss of an IQ point is valuated to
some €3,000–15,000 [3, 4]. The ecosystem services provided by a French forest
provide welfare benefits corresponding to some €970 per hectare [5].
Some cost–benefit analysis (CBA) performed on climate change reach an optimal
level of CO2 concentration in the atmosphere of 650–700 parts per million (ppm)
within a century or two (Weitzman 2009). Furthermore, the whole concept of
assigning monetary values to the above mentioned is for many persons morally
upsetting.
The aim of this chapter is to give the reader a setting (or back drop) to the moral
and theoretical pre-conditions necessary to understand and accept before assigning
monetary values to welfare impacts. After reading this chapter, the reader should at
least understand how, from a philosophical, theoretical and practical point of view,
monetary values of welfare effects can be produced by economists. Monetary values
of welfare effects are crucial for economic planning and the allocation of economic
Are Chemicals in Products Good or Bad for the Society? – An Economic Perspective 111

resources, and the values are being used as decision support when planning for inter
alia health services, infrastructure developments and environmental improvements.
However, in this chapter it is not specifically aimed for the reader to accept the
concept of monetization of welfare effects. Acceptance or rejection is for the reader
to decide.

2 Background Economic Theory Related to External Effects

Damages to human health and the environment are by economists most often
considered as market failures since they are external costs not included in the
price when a transaction is taking place on the market. If the damage were to be
fully financially compensated in the transaction, the damage would not be an
external cost and the market would function properly. A properly functioning
market implies that there is no problem to be solved (from the point of view of
an economist). “Externalities” is the term used by economists when exploring non-
priced effects of transactions [6].
The text above is likely to be a bit unfamiliar to the reader, and to explain the
economic way of thinking we will start from the very beginning.
The economy is in principle inhabited by sellers and buyers. These buy and sell
on a market. They are all utilitarian, which basically means that a moral good is
to maximize pleasure/happiness. A moral bad is to minimize pleasure/happiness
[7, 8]. When related to economic and political decision making, pleasure/happiness
is often translated into “utility” [9]. So what is the decision rationale for the buyer
and seller? And how does the market function?

2.1 The Buyer: Homo Economicus

In the standard neoclassical economic theory, individuals are following a utilitarian
ethical norm and are making decisions as if they are economically rational.
To be a utilitarian implies in the economic area that individual decisions are
being made so as to provide as much utility for the individual as possible. The idea
is then that the sum of utility-maximizing individuals leads to a maximum welfare
for society. The overall idea is that the sum of the decisions taken will maximize
society’s welfare.
Utilitarianism as the root for neoclassical economics has a common basis in
Jeremy Bentham, Adam Smith, James Mill and John Stuart Mill (father and son)
and others. They were influential philosophers and economists in the eighteenth and
nineteenth century Britain [6, 7, 10].
The economic man (homo economicus) is an economically rational individual,
meaning that actions are performed based on the following principles (preferences):
112 S. Åstr€
om et al.

• Preferences are complete (I can compare and rank alternatives).
• Preferences are reflexive (stable).
• Preferences are transitive (I am consistent in my ranking).
Also:
• More is most often better than less (strongly monotonic), although diminishing.
• Utilities can be substituted to some extent (indifference).
The ambitions of the actions are to maximize individual utility (welfare) given a
restricted budget [6, 11].
The economic man is one way of looking at decision making and preferences.
But as should be evident to the reader there are many other ways and theories
explaining human behaviour. Psychologists, anthropologists, sociologists, political
scientists and even engineers all provide their version of human decision making
and preferences. And the philosophers provide thoughts on how humans should
behave. Still, the homo economicus is instrumental for the concept of economic
valuation of environmental and health effects, which is what this chapter is all
about. Why?
Because substitution of utilities allows the homo economicus to receive an
economic transaction as a sufficient compensation for a species being diminished
in numbers; because transitivity allows for comparison and ranking of distinct
environmental end points and other goods/services; because stable preferences
ensure that environmental policies will provide a social good.
The theories on individual decision making from other scientific disciplines tend
to stress factors such as status, social peer pressure, time availability, mood, cultural
aspects, self-affirmation, altruism, and self-perception. as explanatory variables to
decision making [12, 13]. These latter factors are far less favourable for economic
valuation since the value would be unpredictable and varying dependent on
situation. They may, however, provide an equally or even better description of
decision making.
However, economists do try to cope with and interpret some of these factors
affecting human behaviour. Some of this work is done on the concept of donations.
Many theories attempt to explain why people are willing to voluntarily give
money to a public good, and empirical research has been done on this issue. There
are three main theories of individuals’ motives to voluntarily give money to a public
good: altruism, warm glow and conditional cooperation.
People are altruistic, which means that people care about others well-being as
well as their own. An altruistic person likes to help them who help him/her, but also
hurt them who are hurting him/her [14]. Furthermore, when people cooperate
they contribute more to a public good than they would have done with only pure
self-interest. People’s enthusiasm for sacrificing for others diminish if they do not
believe other people is doing their share. By providing public goods by charities,
people feel relieved from guilt and get a warm-glow feeling when making
a donation [15]. According to the theory of conditional cooperation, people are
influenced from others’ donations because of social pressure, social relations and
Are Chemicals in Products Good or Bad for the Society? – An Economic Perspective 113

social norms ([16]; Chap. 1. Kolm, Chap. 3 Schokkaert and Van Ootegem, Chap. 19
Antoci, Sacco and Zamagni). According to Hur [17] people give to charity both to
demonstrate desirable quality and to satisfy their selfishness. Leading social forces
and direction of public policies has an impact in the charity giving.
The discussion above serves to present a very important feature that is necessary
when reading results from CBA performed on environmental impacts.
The ultimate feature of homo economicus, of relevance for this chapter, is
basically that homo economicus can compare welfare with utility with money.
Money can be used as compensation for environmental degradation and
environmental degradation can be translated into monetary losses (and vice versa).
Many objections have been raised against the notion of humans represented as
a Homo economicus. Amongst the objections acknowledged in the economic text
books one can find statements recognizing that it is impossible to measure utility
completely, and that it is impossible to compare utilities of different people.

2.2 The Seller

The seller, or usually the corporation, company, business, or firm acts on similar
principles as homo economicus. While the objective for the buyer is to maximize
utility, the seller tries to maximize profits and/or minimize costs. While the buyers
base their actions on a set of preferences, the sellers base the firms actions as
consequences of mainly three decisions needed:
1. How much of a product to produce.
2. Which production technology to produce.
3. How much production input that is needed.
When the seller has some influence over prices, the price level will also be
subject to a decision [6].
The firm is usually the party responsible for mitigation of environmental impacts
and for taking the costs associated with mitigation. Whether or not these costs are
transferred to the final customer is a topic for another book, but we will stick to
explaining the abatement costs that the seller endures when reducing environmental
impacts.
In general, abatement options are from a bottom-up perspective categorized into
emission control technologies, substitution options or efficiency improvements.
All of these three usually consist of a number of partial costs. Investments,
operation & management costs, fuel prices, labour costs, solvent costs, and in some
cases waste disposal costs are all common costs that has to be taken into account.
There are other relevant options which can be of concern when reducing
environmental impacts. Examples of those are technology substitution, shifts in
production, and also adaptation costs.
From a top–down perspective, the seller can face other types of costs such
as competitive disadvantages or profit losses. These are less direct and also
114 S. Åstr€
om et al.

more difficult to analyse but can nevertheless be important for a cost analysis of
large-scale impacts.

2.3 The Market

The buyer and the seller interact in a place called the market. This is a place that
needs apply to certain conditions in order for it to be a perfectly competitive market
and thereby provide maximum welfare to society (in other words: be effective).
These conditions can be summarized as follows:
1. The sellers produce identical products (homogenous).
2. There are no transaction costs.
3. Both the buyer and the seller have perfect knowledge.
4. Preferences are stable.
5. Only small (relative to the industry) actors that don’t influence market prices
participate (both buyer and seller are price-takers).
6. Market actors can enter or exit the market free of charge.
7. There are no economics of scale.
8. There are no external effects (externalities).
All deviations from these conditions can lead to an inefficient market that no
longer provides maximum welfare to society.
Economic efficiency refers to the use of resources so as to maximize production
of goods and services. One economic system is more efficient than another if it
can provide more goods and services to society without using more resources.
A situation can be called economically efficient if:
• No one can be made better without making someone worse off (Pareto efficient).
• No additional outcome can be obtained without increasing the amount of inputs.
• Production proceeds at the lowest possible per-unit cost.
All of the conditions for an efficient market are being studied in different sub-
branches of economics. Environmental and health impacts are examples of the
violation of the condition “no external effects” which is an area studied mainly by
environmental economists. In other words, environmental problems are to an
economist considered as a market failure, or more precisely a negative externality.

3 Externalities and External Costs

We will now look more deeply into the aspect of externalities and try to explain to
the reader what the term refers to, as well as to present some of the more important
theories relating to externalities.
Are Chemicals in Products Good or Bad for the Society? – An Economic Perspective 115

3.1 Externalities

Externalities can in principle be either positive or negative. A positive externality
may be the result of actions by an individual or a group benefiting others such as
technological spillover, which for instance can be generated by foreign direct
investments in a developing country. The positive externality may also lead to
higher social benefit, being the profit of an activity to an entire society, including
not only the benefit to those members of the society directly involved in the activity,
but also the benefits to all other members.
Negative externalities arise when an action by an individual or a group implies
harmful effects on others such as: unintended dispersion of chemicals to land, air
and water; air pollution effects on health; forest growth; or fish reproduction. When
negative externalities are generated they should be internalized into the market
economy. By internalizing the externalities the economic value of environmental
impacts are allocated to the pollution sources and included in the economics of the
activities causing the problem. This would also allow for the market to function
properly and thereby reach a socially optimal level of environmental impacts.
The problems with negative externalities arise because of market and govern-
ment failures. Market failures occur because markets for environmental goods and
services do not exist, or when the markets do exist, the market prices underestimate
their social scarcity values. However, a market can only exist and function
efficiently when property rights on goods and services exchanged are well defined,
as well as when transaction costs of exchange are small. Basically, from an
economists’ perspective, a part of the problem with environmental degradation
lies in the difficulty to assign property rights to a low-toxic environment, clean air
and water, biodiversity, and a comfortable global atmospheric climate.

3.2 External Costs

External costs, damage costs, also often called just externalities, are a monetization
of negative external effects being the consequences of, for example, some sort of
environmental degradation. These effects and damages are external because the
affected does not receive any compensation and the polluter does not need to pay
for the damage. In order for physical measures of impacts to be commonly
measurable, they must be valued in monetary units. The monetary valuation of
different effects is not a straightforward procedure since many of the effects have
no market value. The total value is often composed of both use values and non-use
values.
External costs have to be considered and included in prices in order to give the
product their real cost. One way to include external costs is to follow the Polluters
Pay Principle (PPP). The PPP state that the polluter should bear the cost of policy
116 S. Åstr€
om et al.

measures and also ensure that the environment is in an acceptable state. According
to PPP, polluters bear the full financial responsibility for pollution reduction.

3.2.1 Damage Costs ¼ External Costs

Often in literature one comes across the term damage costs. Damage cost is in some
cases expressed as something different than external costs. However, we want to
stress that damage costs are either equal to, or a part of external costs. In principle,
damage costs can be a subset of internal costs, but as such it serves little meaning to
explicitly identify it as the impact of the cost is already properly allocated. Other
meanings of damage costs are basically just misunderstandings of the concept.
Another expression often used to describe an externality is the term social costs, as
in contrast to private costs.

3.2.2 Private and Social Costs

In general, economic inefficiency in resource allocation would be the result of a
divergence between private benefits or costs and social benefits or costs, i.e. the
result of externalities. Private costs (or internal costs) are directly taken by the
buyer. Private costs for a transport user would, for example, include expenses for:
wear and tear, energy cost of vehicle use, transport fares, taxes and charges, as well
as welfare effects such as own time costs.
Social costs reflect in this example all costs occurring from the provision and the
use of transport infrastructure, such as wear and tear costs of infrastructure, capital
costs, congestion costs, accident costs and environmental damage costs. Some of
these costs are already indirectly included in the private costs through taxes and
charges, while others are not. In the context of environmental economics, private and
social aspects are of importance. Mainly since it is often the case that environmental
degradation is a social cost caused by private activities. Hence, the distinction
between private and social is as presented above another impact of costs not being
properly internalized in prices.

3.3 Theories for Avoiding Welfare Losses

As a repetition, environmental degradation is usually a negative externality from,
for example, the use of chemical additives, which cause a market failure, which in
turn lead to welfare losses. If this is the case, and welfare loss is a bad thing, then
something should be done about it. We have earlier presented the PPP as one way of
correcting the market failure and we here present two other theoretical
constructions to how market failures can be counteracted or avoided.
Are Chemicals in Products Good or Bad for the Society? – An Economic Perspective 117

3.3.1 Pareto Efficiency

Pareto efficiency, also known as Pareto optimality, is named after an Italian
economist, Vilfredo Pareto (1848–1923). The definition of a Pareto efficient
economic system is that no re-allocation of given goods can be made without
making at least one individual worse off (there is no way to make any person better
off without hurting anybody else). Pareto improvement from a non-efficient system
is achieved when a change to a different allocation makes at least one individual
better off without making any other individual worse off [Varian 47].

3.3.2 The Kaldor–Hicks Compensation Principle

Two economists, Nicholas Kaldor (1939) and John Hicks (1940), authored the
Kaldor–Hicks compensation principle (also known as Kaldor–Hicks criterion),
which is a measure of economic efficiency.
According to the Kaldor–Hicks compensation principle, an outcome is more
efficient if those that are made better off could (in theory) compensate those that are
made worse off. However, the Kaldor–Hicks compensation principle does not
require the compensation to actually be paid, just that the possibility exists [18].

3.3.3 The Coase Theorem

Another theory is the Coase theorem. The theorem specifies the need for property
rights in order to achieve economic efficiency. Property rights, in the context of
environmental degradation, relates to the right to have a certain level of environ-
mental quality. The Coase theorem basically states that the original distribution of
property rights doesn’t matter if the following criteria apply:
1. Everyone has all information needed.
2. Consumers and producers are price-takers.
3. There is a costless court system for enforcing agreements.
4. Producers maximize profits and consumers maximize utility.
5. There are no income or wealth effects.
6. There are no transaction costs.
If these six criteria apply, the market for property rights (environmental
endowments) is efficient [18].
118 S. Åstr€
om et al.

4 Valuating Externalities

Having explored the term externalities and its implications, this chapter presents
methods used to assert economic values to externalities related to environmental
impacts.

4.1 Economic Values at Stake

In order for various environmental impacts to be measured on a single scale, they
must be valued in monetary units. The monetary valuation of different effects is not
a straightforward procedure since many of the effects have no direct market value.
To set a “total” value on the environment, relevant values are divided into three
groups: use values, option values and non-use values.
Use values are defined as the utility one person gains from using the good or
service, for example walking in the forest or fishing. This use value includes direct
and non-direct values. The direct use value is the value attributed to direct utiliza-
tion of ecosystem services. Non-direct-use value or “functional” value relates to the
ecological function performed, e.g. by forests, such as the protection of soils and the
regulation of watersheds [19].
Non-use values, also referred to as passive use values, come from the utility an
individual gain even if they never intend to use the resource by themselves. The
non-use value includes: option value (the value of having the option to use the
resource/service), existence value (the value of knowing something exists), altruis-
tic value (the value of knowing that someone else gains utility) and bequest value
(the value of passing environmental resources to future generation even though they
never use it or intend to use it). The option value consists both of use and non-use
values. The bequest value is similar to the altruistic value and contains both use and
non-use values [18].
Figure 1 summarizes the welfare values presented above. It also lists the valua-
tion methods suitable for the calculation of monetary values.
As is seen in the figure, the different economic values need different methods for
economic valuation.

4.2 Methods to Valuing Externalities

There are two main scientific areas in which economic valuation takes place,
environmental economics and ecological economics. The main difference between
the two areas is whether or not the general description of how the economy
functions is accepted or not. Environmental economists do basically accept the
way the market functions and homo economicus (Sect. 2). Ecological economists
Are Chemicals in Products Good or Bad for the Society? – An Economic Perspective 119

Fig. 1 Summary of economic welfare values related to environmental impacts and valuation
methods applicable for the values [20]

have a different approach to the market function and express (inter alia) the need for
alternative ways to express the usage costs and value of natural resources [21].

4.2.1 The Environmental Economics Approach

The main challenges of environmental economics are to develop methods for
definition and valuation of externalities that are consistent with mitigation costs
associated with the externality in question.
Consistency is achieved by deriving a demand function for the non-market good
or service. The demand function is derived by researching the Willingness To Pay
(WTP) money for obtaining an environmental good or service. Alternatively,
studies derive the Willingness To Accept (WTA) monetary compensation for losing
an environmental good or service. The purpose of measuring WTP is to estimate a
change in welfare because a change in welfare is not directly observable [19]. The
current preferences of the survey population state the current price (WTP/WTA),
given their awareness of the subject and the information available. The derived
value mirrors the current attribute and preferences, rather than the importance of the
environmental impact. The result can be compared to the values of marketed
commodities [22]. As a reminder, the value of a market commodity is seen in
its price.
120 S. Åstr€
om et al.

Basically, economic valuation is performed by two different main methods. You
either observe indirect statements of economic value ¼ Reveal preferences. Or you
ask individuals for their economic value ¼ State preferences. One important aspect
to have in mind is that valuation is performed to identify demand for resources and
services for which there is no functioning market [18].
The stated preference method is a direct approach and is used in order to value
both use values and non-use values by using a hypothetical market. The choice
experiment (CE) and the contingent valuation (CV) methods are the two most
common examples of stated preference methods. In the CE method the respondents
are asked to choose a level of environmental quality from a set of varying environ-
mental qualities, called choice set. In the CV method the respondent is asked to
imagine an environmental market situation and is then asked how she would act in
that given situation. CE and CV attempts to find the WTP for a good or service by
asking individuals direct questions about their preferences. Alternatively,
researchers can ask the respondents for their WTA.
The main criticism towards the stated preference method is that the conclusions
are drawn from a hypothetical survey, where the respondents who state they would
pay a certain amount do not actually have to pay at all.
The revealed preference method is an indirect approach that is used in order to
monetize use values. This method observes the real choice between money and the
environmental goods. Methods often include observations of consumers’ or
producers’ behaviour or actions, such as the hedonic price method and the produc-
tion function method. The hedonic price method determines values from actual
market transactions. These transactions are used to see how the price of a market
commodity varies when a related environmental good changes, such as the effects
of noise or air pollution on house prices. The production function method is used to
estimate the value of the environmental effects on production. This method is
suitable when consumption or production of a private good is affected by the
environmental good. An example is the valuation of ground-level ozone levels by
valuing the impact on the production of wheat or timber, which has market prices.
The problem with the revealed preference method is that it does not contain all the
individuals’ values that affect the WTP.
One solution to the problem with hypothetical markets is to actually create a
market with real payments where theories can be tested in a controlled setting.
Experimental markets can take place either in a laboratory experimental market or
in a realistic setting, such as a field experiment. In a field experiment the researcher
construct a market where an environmental or public good is offered and real
payment can take place in order to receive the public good [18]. However, natural
field experiments are hard to construct because they generally require that the goods
are excludable and rival, and that a similar market does not already exist.
Another method used at times is the Standard price method. This method
presents environmental values as corresponding to the mitigation costs needed to
avoid environmental degradation. The main disadvantage of this method is that the
environmental value derived is poorly linked with the environmental impact.
Are Chemicals in Products Good or Bad for the Society? – An Economic Perspective 121

Another approach often used is to transfer and adjust results from other related
studies, a so-called Benefit Transfer. This procedure is often used since making
new, locally adapted studies is expensive and time consuming.

4.2.2 Methods to Valuing Health Effects

In the case of health effects, other methods than stated or revealed preference
methods are often used to estimate the impact of externalities and valuating the
human health damages. Both productivity losses and costs for hospital admissions
or other hospital-related activities are used to monetize health effects. Of special
importance for the valuation of health effects are the metrics “Value of a Statistical
Life”/“Value of Prevented Fatality” (VSL, VOSL or VPF) and “Value of a Life
Year Lost” (VOLY).
VSL is derived based on the monetary sum people are willing to pay for reducing
the risk of fatality. An example of a suitable monetary sum is the price premium for
a safe car, which together with risk reduction estimates for the safe car is sufficient
to calculate a VSL. The WTP for Ds (the change in the risk to die) leads to the value
of statistical life such as:
X
VSL ¼ WTPi =DsN;
i

where i is the conditional probability to live to age i for a person of age a, N is the
population at risk.
VOLY is most often linked directly with VSL. Within the ExternE project for
instance, VSL is expressed as equal to the discounted value of VOLY [2]. Hence

X
T
VSL ¼ VOLY ðaPi =ð1 þ rÞia Þ;
i¼a

where aPi is the conditional probability to live until year i for a person at age a, T is
the maximum expected life length and r is the discount rate.

4.2.3 The Ecological Economics Approach

Environmental economists and ecological economists work in very similar fields but
with some differences that it might be useful for the reader to know about. Ecological
economics can be defined as “the field of study that addresses the relationship
between ecosystem and economic systems in the broadest sense” [23]. While the
ecological economist has a biophysical view of value, the environmental economist
states that the value cannot be reduced to a simple physical metric [18].
122 S. Åstr€
om et al.

As a simplification, environmental economists usually value changes in ecosystem
services. An example of such a change is fresh water degradation of any kind.
Ecological economists, on the other hand, rather value the stock of ecosystem services
or goods. The corresponding example would be the value of water. Alternatively, one
can say that environmental economists usually monetize marginal changes, while
ecological economists value stock existence values.
For instance, Costanza et al. [24] estimated the value of 17 ecosystem services in
16 biomes to an average US$33 trillion (12 zeroes) globally. This value is almost
twice the size of the compared global GDP (or Global Gross National Product to be
precise). The ecological economists estimate these values so that ecosystems and
biodiversity can be included in new calculations of economic efficiency and
economic performance.
The background methods used for valuing ecosystem services are often similar
for ecological and environmental economists. The valuation methods are presented
earlier in this chapter.

5 Limitations with Economic Valuation

There are a number of concerns related to economic valuation of environmental
impacts and health effects. These concerns are often valid and need to be stated
explicitly so that a process of continuous improvements can be assured.

5.1 Valuation Methodology

The Stated preferences method is a controversial method and well debated between
economists. The main criticism towards the Contingent Valuation (CV) method is
that the elicited values and people’s WTP is based on hypothetical answers and not
real economic decisions and thereby meaningless because people are not facing real
payments or a real budget constraint [18].
There are some biases concerning the stated response to WTP questions. Some
responses might be from “yes-sayers” to please the interviewer. Others might give
“protest zeros” responses, if the respondent disagree with the conducted scenario.
While yet others desire a “warm-glow” since the respondent has a moral satisfaction
from the act [25].
Another part of the debate concern a more philosophical approach, it discusses if
passive use values or existence values should be included in economic analysis. The
more traditional view emphasizes the necessity for a good to be physical or at least
observable in order to get utility from buying it. In the non-use values, consumers get
utility from a good without utilizing it physically. According to Diamond and
Hausman [26], the CV method should not be used in CBA or damage assessment.
They argue that WTP estimates from the CV method are not measurements of
Are Chemicals in Products Good or Bad for the Society? – An Economic Perspective 123

preferences for environment resources since it is difficult to compare the hypothetical
responses with real economic choices.
Also, and this is a fairly economic discussion, one can be concerned with most
valuation studies usually using income as the budget constraint. The income is a
“flow” value while this flow is sometimes compared to “stock” values (i.e. natural
resources). If the income were compared with the growth in stock, then this
objection turns invalid.
A general critic against all the valuating methods, and the entire field of
environmental economics, consists of whether it is possible and fair to put an
economic value on the environment [27].

5.2 General Concerns Related to Economics

As we hinted in part 2 of this chapter, there are concerns with using the traditional
neoclassical economics view of homo economicus as an expresser of welfare
impacts. Not all persons can or wish to translate welfare into utility into money,
and not all would be willing to accept monetary compensation out of moral reasons
(these respondents are usually sorted out of WTP surveys as protest answers as we
described earlier in this text).
There are also more fundamental problems. The problems of highest concern for
the authors relate to: the existence of a utilitarian moral; preferences for decision
making and the function of the market.
The utilitarian man is a basis for decision making in economics. And it is a
description that is valid in most market situations in the western societies at least.
But, the utilitarian ethics is something that few other social sciences can find as
rational for human decision making outside the usual market setting, as described
earlier.
That the preferences are complete is an important statement for rational decision
making but a preference that can be difficult to replicate in environmental valuation
studies. It is basically very difficult to compare cleaner air with otter preservation
with the purchase of a car with avoidance of cancer with reduced fish populations.
In other words, preferences for environmental goods and services are likely not to
be complete.
There are also concerns related to preferences being stable, which they quite
often aren’t.
Furthermore, and this is linked to the complete preferences, the hypothetical
market environmental goods and services is not a market under perfect competition.
The existence of externalities is one reason for this, which is why environmental
economists try to value externalities. But the condition of perfect knowledge isn’t
there either. The reason is simple; we still don’t have all the information about
environmental degradation and risks associated with the use of, for example,
chemicals.
124 S. Åstr€
om et al.

Nevertheless, economic valuation is still the best available option when trying
to allocate resources to protect the environment or human health. Why?
Because some sort of valuation and ranking of options always have and always
will take place in decision making. The choice is between using economic values
derived in a consistent and transparent way (environmental economics approach),
or to use arbitrary and random economic or other values estimated in a case-by-case
setting. And the authors of this chapter are in favour of a transparent approach that
is open for improvements.

6 Identification of Impacts and Their Stressors

When a chemical is emitted to the environment, it is distributed into different
environmental matrices depending on the properties of the substance. When
distributed in the environment, different organisms, including humans, can be
exposed to the substance via different exposure routes such as ingestion, inhalation
and dermal exposure. Depending on both species and substance characteristics, the
exposure to a substance can give rise to different impacts.
In this section, the process of identifying impacts and the substances causing the
impacts, here called stressors, will be discussed in more detail.

6.1 Impacts on Human Health and the Environment

When identifying impacts to human health or the environment and their stressors,
there are two main approaches that can be used. One of these approaches focuses on
the emission of a substance, called stressor, and tries to determine which impacts
that can occur due to the emission of the substance (stressor to impact). The other
approach instead focuses on an observed impact and tries to identify which stressor
that caused the impact (impact to stressor).

6.1.1 Stressor to Impact Approach

The stressor to impact approach is used when the impact of a substance is unknown.
It is, for example, used in the guidance on information requirements and chemical
safety assessment developed by the European Chemicals Agency [28] for the
implementation of REACH.
When determining the impact of a stressor using this approach, there are two
main steps, exposure assessment and hazard assessment [28]. The exposure assess-
ment is aimed to determine the concentrations of a substance that a certain organism
can be exposed to due to the emission of a certain amount of a substance. The first
step is the release estimation. The release estimation aims to determine how much of
Are Chemicals in Products Good or Bad for the Society? – An Economic Perspective 125

a substance that is emitted, where the emission takes place, to which environmental
matrices and how the emissions are distributed over time. Next, the environmental
fate of the emitted substance is determined using multimedia environmental models
which are based on substance characteristics as well as the properties of the
receiving environment [29]. Depending on which type of model used, the environ-
mental fate can be determined with different level of detail. Finally, exposure
estimation is performed where it is determined which organisms that can be exposed
to the emitted substance and in what concentrations.
The second step when determining impacts is the hazard assessment [28].
During the hazard assessment, the impact caused by the exposure to a substance
is determined [30]. This is often done using in vitro or in silico testing. The results
of the hazard assessment are often presented as dose–response functions.
For more information on exposure and hazard assessment, see ECHA [30–34].

6.1.2 Impact to Stressor Approach

The impact to stressor approach is used when an impact has been observed but
the stressor causing the impact is unknown. This approach is often used when
studying impacts on human health, for example within the field of epidemiology.
This approach is the backwards version of the stressor to impact approach. Here, the
impact is known. Here, the stressor is identified by studying the affected organisms,
for example their daily routines, their food intake or by sampling their surrounding
environment for possible stressors.

6.2 Economic Impacts

Some environmental degradation can actually be bad for business. The classical
example is the laundry firm sited right next door to the coal power plant. Environ-
mental degradation does often have these types of impacts which need to be
quantified. Economic impacts can be either large-scale or small-scale impacts.
Examples of large-scale impacts are loss of work hours and loss in productivity,
investment in cleaning equipment, etc.

7 Economic Tools for Analysis

Valuation of environmental impacts can consist of both monetary values and non-
monetary weights to make it easier to estimate total effects from different products
and projects.
126 S. Åstr€
om et al.

7.1 Cost–Benefit Analysis

In CBA both cost and benefits are given a monetary value and then compared.
Effects on, e.g. the environment, time use and health are examples of externalities
that are monetized in a CBA. These are then compared with technical abatement
costs, etc. in order to calculate net benefits of the studied scenario or policy. By
doing this, the analysis provides policy relevant results describing whether a
scenario provides a net benefit for society or not. The analysis can also identify
the most beneficial scenario out of a number of scenarios.
A CBA usually considers all costs and benefits to the society as a whole.
The value for society of a studied scenario or policy is described by the net social
benefit (NSB):

NSB ¼ B  C;

where B is social benefits and C is social costs.
The major steps in a CBA are usually [35]:
1. Specify the set of alternative projects/programs
2. Decide whose benefits and costs count (stakeholders)
3. Catalogue the impacts and select measurement indicators (units)
4. Predict the impact quantitatively over relevant time period
5. Monetize all impacts (convert all costs and benefits)
6. Discount benefits and costs to obtain present values (discount rate)
7. Compute the net present (NVP) of each alternative
8. Perform sensitivity analysis
9. Make a recommendation based on the NPV and sensitivity analysis

7.2 Impact Pathway Approach

The impact pathway approach was developed within the ExternE project series and
is commonly used today to assess transport externalities [2]. The method is a bottom-
up approach in which environmental benefits and costs are estimated by following
the pathway from source emissions via quality changes of air, soil and water to
physical impacts, before being expressed in monetary benefits and costs. The impact
pathway approach is acknowledged as the preferred approach when it comes to air
pollution and noise costs. Figure 2 shows the impact pathway methodology, whose
principles are: emissions and inventories, dispersion modelling of the emissions,
exposure calculation to the emission calculations involving the impact calculation
on human and ecosystem of the emissions, and external costs calculation of damage.
To illustrate the concept of external (or damage) cost, we can first look at the
emissions from Waste of Electric and Electronic Equipment (WEEE) to the air. The
different points leading to the evaluation of emission’s impact are the following [36]:
Are Chemicals in Products Good or Bad for the Society? – An Economic Perspective 127

SOURCE
(specification of site and technology)
emission
(e.g. kg/yr of particulates)

DISPERSION
(e.g. atmospheric dispersion model)
increase in concentration at
receptor sites
(e.g. µg/m3 of particluates
in all affected regions)

Dose-
DOSE-RESPONSE FUNCTION Response
(or concentration-response function) Function
IMPACT

impact
(e.g. cases of asthma due to ambient
concentration of particulates)

DOSE

MONETARY VALUATION
cost
(e.g. cost of asthma)

Fig. 2 The impact pathway approach [2]

1. Emissions and inventories are in the case of air pollution related to the assess-
ment of the level of pollutants released from various sources. That is to say
emission specification of the relevant technologies and pollutants. The determi-
nation of emission factors of different substance in WEEE road transport is often
the product of national, EU and international research.
2. Dispersion modelling of the emissions concerns how air pollutants disperse in
the ambient atmosphere. This step is also called environmental fate analysis,
especially when it involves more complex pathways that pass through the food
chain. The pollutants dispersed to the atmosphere are in general modelled using
dispersion models.
128 S. Åstr€
om et al.

3. Exposure calculation to the emission calculations involving impact of emissions
on humans and ecosystem of the emissions means the impact calculation of the
dose from the increased concentration. The impact calculation is followed by
calculation of impacts (damage in physical units) from this dose, using a
dose–response function. The impact of WEEE substances on health and the
environment is location specific and is based on conditional, that is to say
the way the WEEE is taken care of. Hence, the exposure assessment relates to
the population and the ecosystem being exposed to the externalities.
4. Impact: the exposure response relations are based on epidemiological studies.
5. External cost of damage is where economic valuation of these impacts i.e.
external costs and their value is performed [2]. Evaluation of impacts on both
the humans and the ecosystem is based on valuation studies, in order to monetize
the external effects.
The ExternE methodology has been applied on many studies analysing environ-
mental, energy and transport policies, both at a national and European level. The
relevance on transport externalities has been focused on emissions, dispersion
modelling and updating of dose–response functions. Noise and accidents have
also been analysed in addition to air pollutions. With this method, aggregated
external cost in addition to marginal external cost of transport can be estimated.
The external cost estimations from the transport sector are depending on the mode
of the transportation in question and where it takes place since the emissions
released differ as well as the location of the emissions [2].

7.3 EPS Method

The EPS (environmental priority strategies in product design) system was initiated
in 1989 by Volvo Automotive Company, IVL Swedish Environmental Research
Institute and the Swedish Industry Federation. The current version was developed at
the Centre for Environmental Assessment of Product and Material Systems (CPM)
[37, 38].
The EPS system was initially developed to be used within the product develop-
ment process as a tool to help assess the environmental performance of products. The
system is based on LCA (Life Cycle Assessment) methodology and uses inventory
data (kg of substance X), characterization factors (impact/kg of substance X) and
weighting factors (cost/impacts) to calculate the external costs or values of a product.
By multiplying the characterization factor with the weighting factor, an impact index
is obtained (cost/kg of substance X) which describe the cost/values related to the
emission per use of a kg of a certain substance.
The first version of the model was developed in 1991–1992. In the EPS system,
the impacts are expressed in terms of socio-economic costs (or values) occurring by
unit effects of damage to five safeguards subjects: human health, biological diver-
sity, ecosystem production, natural resources and aesthetic values. The latest
version was published in 1999 [37, 38].
Are Chemicals in Products Good or Bad for the Society? – An Economic Perspective 129

For abiotic stock resources, the resource value is set as equal to the production
and environmental cost for a sustainable alternative. For fossil oil, gas and coal,
these alternatives are rapeseed oil, biogas and charcoal, respectively. For metal
(metal ores), the production and environmental costs to upgrade low-quality ores
(sustainable supplies), such as silicate minerals, to a quality similar to present day
ores, using a bioenergy-driven process (near-sustainable process), is used as the
resource value.

8 Examples of Valuation of Impacts

In order to illustrate how the results finally turn out, examples for external costs
induced by lead emissions and environmental and human health end points are
presented here. The example presenting the external costs of lead emissions is more
elaborate so as to give the reader an opportunity to follow a typical line of
reasoning, while the generic table on typical external costs can be used as examples
of final results from economic valuation studies.

8.1 Economic Valuation of Lead Emissions

Lead (Pb) is used for many applications, for example in electronic goods such as
cathode ray tube (CRT) televisions and as a stabilizer in PVC. Pb is one of the
oldest known and most studied occupational and environmental toxins. Despite the
many studies, there is still debate regarding the toxic effects caused by Pb [39].
In studies of acute effects on humans caused by exposure to Pb, nephrotoxic
effects as well as gastrointestinal effects have been observed [40]. Encephalopathy
can affect both children and adults. Acute encephalopathy has been shown to
increase the incidence of neurological and cognitive impairments.
Chronic exposure to Pb has been shown to cause anaemia, neurotoxic effects,
such as reduced cognitive performance and reduced peripheral nerve conduction
velocity, and nephrotoxicity. Children are more sensitive to exposure to Pb than
adults, especially during the first 2 years of life [41]. For children, exposure to lead
can cause growth retardation, affect the neuropsychological development and cause
encephalopathy [39]. Adverse reproductive effects due to lead exposure have been
observed for both men and women. Exposure of pregnant women to low
concentrations of lead is associated with miscarriages and low birth weights [40].
According to Spadaro and Rabl [41], damage costs of IQ decrement is likely the
dominant part of the total damage costs of Pb. The dose–response function has been
quite well characterized for Pb, for example by Schwartz [48] in a meta-analysis,
who found that the IQ decrement is 0.026 IQ points for a 1 mg/L increase of Pb in
blood. Spadaro and Rabl identified two possible ways of linking blood levels of lead
to exposure. One of the methods connects incremental exposure of Pb in air to
130 S. Åstr€
om et al.

Table 1 External costs for loss of IQ points
Endpoint Unit External cost Reference
Severe nuisance ELU/person-year 10,000 Steen [38]
Loss of one IQ point €/IQ point 3,000 Lutter [3]
Loss of one IQ point €/IQ point 8,600 GREENSENSE project,
2004 cited in Spadaro
and Rabl [41]
Loss of one IQ point €/IQ point 10,000 Spadaro and Rabl [41]
Loss of one IQ point €/IQ point 14,500 Grosse et al. [42]
Loss of one IQ point €/IQ point 15,000 Muir and Zegarac [4]

increases of Pb in blood levels, while the other method relates blood levels to
ingested dose of Pb.
Combining the dose–response function with the exposure/blood level relations,
Spadaro and Rabl [41] derived two possible characterization factors of 0.268 and
0.59 IQ points decrement per kg emitted Pb.
External costs for loss of an IQ point have, for example, been derived by Lutter
[3], Grosse et al. [42], Muir and Zegarac [4], see Table 1. The range of external
costs for the loss of one IQ point was estimated to 3,000–15,000 €/IQ point. Using
an average of 10,000 €/IQ point in combination with the two characterization
factors given above, as in the study by Spadaro and Rabl [41], gives a damage
cost of 2,680–5,900 €/emitted kg Pb. External costs for emission of lead were also
derived in the EPS system [38]. Damages caused by emissions of Pb were estimated
with IQ decrement. In the EPS system the loss of IQ points is classified as severe
nuisance which is measured in YOLL (person-years). A Swedish case and a global
case were derived. The Swedish case was based on Swedish emission data and
epidemiological data from 1990. Based on the Swedish case, a characterization
factor of 1.58  104 person-years/emitted kg Pb is obtained. For the global case,
global emissions for 1983 estimated by UNEP [43] and epidemiological data from
USA were used. These data yield a characterization factor of 0.291 person-years/
emitted kg Pb. According to the EPS system, the cost for severe nuisance is
10,000 €/person-year. This gives a damage cost of 1.58–2,910 €/emitted kg Pb.
The Swedish value is considerably lower than the external costs derived by Spadaro
and Rabl [41], while the global estimation is very close to Spadaro and Rabl’s
estimations.

8.2 Example of Economic Valuation Results Linked
to Environmental and Health End Points

Table 2 presents results from three different methods and studies that have
performed large-scale inventories on external costs associated with environmental
and human health impacts [37, 38, 44, 45]
Are Chemicals in Products Good or Bad for the Society? – An Economic Perspective 131

Table 2 External costs for different environmental and human health impacts
Safeguard EPS LIME ExternE
object Endpoint Unit (Euro/unit) (Euro/unit) [Euro2000]/unit
Human health Life expectancy YOLL 85,000 40,000
Life expectancy DALY 97,000
Fatal cancer due to Case 1,120,000
radio nuclides
Value of prevented Case 1,500,000
fatality
Cough days Case 38
Work loss days Day 295
(WLD)
Severe nuisance YOLL 1,000
Ecosystem Crop growth kg 0.15 0.093–0.237
production capacity
capacity Fish production kg 1
capacity
Biodiversity Species extinction Per specie 1.10E+11
Species extinction Per specie 4.8E+10

8.3 Illustrative Cost–Benefit Analysis of Flame Retardants
in Furniture

Let us consider the use of flame retardants in furniture, which has been a standard
additive approximately since the 1970s. Flame retardants are added to reduce
flammability and therefore to prevent fire. In Sweden there should be some 6 million
couches which we will use for this simple example. Each couch needs some 0.5 kg
of flame retardant.
It is assumed that the annual life years gained from using flame retardants equal
X (external benefits). And the value of each life year lost avoided is €40,000 [45].
The costs of using flame retardants equal the extra production costs, are assumed
to some 4 €/kg.
The external costs of using the flame retardants are caused by long-term adverse
impacts in the aquatic environment (reduction in fish production capacity) and
severe nuisance in humans (T) and potentially disturbance in human development
(Z). There are as of yet no economic values derived for the latter two but we express
the values as Y and U. For reduction in fish production capacity the value from the
literature is 1 € per kilogram fish [37, 38]. And in our example, we assume that the
production capacity is reduced by some 10 tonnes of fish.
The CBA then shows that flame retardants are good for society if:

40000X > 4  0:5  6000000 þ 10000  1 þ T  Y þ Z  U:
132 S. Åstr€
om et al.

Our example also shows that the T, Y, Z and U need to be estimated in order
to see the welfare impact of using flame retardants in furniture. See this as a call
for data.
Since flame retardants have been recognized as not desirable (although not
properly quantified in economic valuation), there is now work on replacing flame
retardants with other additives with the same functionality.
The substitution of flame retardants is assumed to cost some 8 €/kg substitute
and the substitute is equally effective with respect to decreasing flammability.
Assuming that equal mass of additives is needed, the CBA shows that it is good
for society to replace flame retardants in furniture if:

ð8  4Þ  0:5  6000000 < 10000  1 þ T  Y þ Z  U:

Note that the cost for life years is left out of the equation since the impact on fire
is the same between the two types of flame retardants.
CBA can be used also when the definite outcome is unknown but when there are
estimates. The T and Z in the equation might be two possible outcomes with
different prices (Y and U). Pretend that the probability of T is 0.3 and that the
probability of Z is 0.7. The equation above would then be

ð8  4Þ  0:5  6000000 < 10000  1 þ 0:3  T  Y þ 0:7  Z  U:

where 0.3  T  Y þ 0.7  Z  U is equal to the expected value of the environ-
mental and human health impacts considered.
As is seen, this example shows that flame retardants might be good for society
(from a socio-economic perspective) even if they cause a number of adverse
environmental and human health impacts as long as the value of the avoided
mortality impacts is larger. Replacement of flame retardants should only be done
(from an economic perspective) if the replacement cost is smaller than the avoided
environmental and human health values.

9 Discussion

Economic valuation of environmental and human health impacts is one tool avail-
able for the management of chemical additives in society. There are other tools, but
it is mainly economic tools that give an answer to whether it is good or bad for
society to perform a certain action. One might not agree with the moral code
supporting utility and profit maximization, but it is a moral code of sort. It thereby
allows for the economic tools such as CBA to provide answer on what is the right
course of action. It also stresses the importance of inclusion of all parameters
related to the benefits and costs associated with the use of chemicals. Chemicals
are serving society with a number of positive functions, and these must be taken
into account when performing CBA.
Are Chemicals in Products Good or Bad for the Society? – An Economic Perspective 133

A strong focus on estimating external costs from chemicals is motivated since
there has been a severe lack of information and knowledge in this area, but the
external costs must be complemented with benefit assessment in order for a CBA to
provide a useful result. An external cost estimate only provides partial results and
should not be used as policy support in itself.
As we have pointed out in this chapter current economic methods and back-
ground assumptions leave room for substantial improvements. And improvements
are being made in all areas, although it takes time for these improvements to enter
into the applied versions of economic analysis. But larger attention is definitely
needed for analysis based on other assumptions than utility-maximizing behaviour
where the preferences are complete and stable and where all actors on the market
have perfect knowledge.
The negative aspects of chemical additives appear to be getting more and more
attention in the public debate. Results linking chemical additives to adverse envi-
ronmental and human health impacts are being produced. But more results are
needed. More economic valuation studies are needed to support analysis as well as
impact analysis on parameters such as human fertility, animal reproduction and
animal productivity. Of big concern for the authors of this chapter is the need to
know more about diffuse exposure from the use of products containing chemical
additives.
Also, and this is where it gets very tricky, stressors are likely to be influencing
each other. In other words, there is a possibility that “cocktail effects” exists. These
“cocktail effects” are likely caused by a large number of lifestyle factors (food
intake, stress, sleep, exercise, socio-economic factors, status) as well as by
pollutants (air pollutants, water contaminants, diffuse exposure to chemicals).
More knowledge is desperately needed about the potential existence of “cocktail
effects”. Current limit values of chemicals and other pollutants are usually derived
from a single-pollutant impact measurement, but in reality humans are exposed to
all of the above-mentioned factors to varying degrees. So sensibilities to chemicals
derived from a laboratory environment might understate the “real life” sensibility to
the same chemical. Identification and quantification of “cocktail effects” are the
major challenges for both the scientific and economic research communities.

10 Buzz Words

Table 3 summarize a number of terms that often occur in the context of economic
valuation.
134 S. Åstr€
om et al.

Table 3 Buzz words within environmental economics
Buzz word Quick explanation
YOLL (years of life lost) The number of deaths caused  the standard life
expectancy at the age of death
YLD (year lost due to disability) The number of incidents  disability weighting factor 
the average duration of the case until remission or
death
DALY (disability adjusted life year) How many years of life that is lost due to premature death
and morbidity. Normally: DALY ¼ YOLL + YLD
QALY (Quality adjusted life year) Years that would be saved following an intervention
HALY (health adjusted life year) A generic term that includes the two most popular
measures, the QALY and the DALY [46]
VSL (value of statistical life)/value The monetary welfare average value assigned to not
of prevented fatality (VPF) dying prematurely
Dose response function The relation between experienced dose and
environmental and human response
Exposure response function The relation between exposure to an environmental
stressor and the environmental or human response
Stressor Substance causing adverse environmental and/or human
health impact

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RISKCYCLE and EU Legislation

Uwe Lahl and Barbara Zeschmar-Lahl

Abstract RISKCYCLE is an artificial word which addresses the risks associated
with the global recycling streams. As part of materials like waste paper, plastic, and
electronics, pollutants and chemical additives are transported abroad, e.g., they are
exported to emerging and developing countries. Here these pollutants/additives can
cause risks for humans and the environment especially if treatment/recycling is
performed on a lower technical standard. The specific risks that can occur have been
studied in an international EU-funded research program, which is the basis of this
publication.
At the end of such a project with important results, it is also the question: How
can these results become part of a solution for this problem? For this purpose we
have analyzed, which EU regulations have the ability to cover RISKCYCLE,
namely for waste (WEEE, RoHs), product design (ecodesign), and chemicals
(REACH). Finally, all regulations contain segments that are suitable to address
RISKCYCLE. But the European chemicals legislation is the best sector to integrate
the RISKCYCLE problem because of its sophisticated instrumental equipment.
It is shown that REACH today in principle has already many necessary
instruments to tackle RISKCYCLE. So within the registration procedure of
chemicals, the registrants have to include RISKCYCLE exposure scenarios. The
guidance documents for the registration procedure cover the waste sector in a way
that risks identified in connection with waste export in developing countries should
be quantified and if necessary managed. But it is open, how these provisions are
considered in reality.

U. Lahl (*)
Technical University Darmstadt, Institute IWAR, Petersenstr. 13, 64287 Darmstadt, Germany
e-mail: uwe.lahl@web.de
B. Zeschmar-Lahl
BZL Kommunikation und Projektsteuerung GmbH, Oyten, Germany

B. Bilitewski et al. (eds.), Global Risk-Based Management of Chemical Additives II: 137
Risk-Based Assessment and Management Strategies, Hdb Env Chem (2013) 23: 137–152,
DOI 10.1007/698_2012_202, # Springer-Verlag Berlin Heidelberg 2012,
Published online: 24 November 2012
138 U. Lahl and B. Zeschmar-Lahl

Therefore the authors give some recommendations, how within REACH
RISKCYCLE aspects could become a more binding part of the regulation.

Keywords Legislation, REACH, Recycling, RISKCYCLE, Waste exports, WEEE

Contents
1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
2 Ecodesign Directive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
2.1 Basics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
2.2 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
3 Waste Legislation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
3.1 Basics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
3.2 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
4 REACH: The European Chemicals Legislation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
5 REACH and RISKCYCLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
5.1 REACH Regulations on Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
5.2 REACH Regulations on Recovered Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
5.3 REACH Regulations on Waste Life Cycle Stage of Substances . . . . . . . . . . . . . . . . . . . . 144
5.4 Risk Management Measures of Exposure Scenarios . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
5.5 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
6 Prospect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151

1 Background

While analyzing the outcome of RISKCYCLE project [1] one of the main points
noticed is that selected hazardous pollutants (chemical additives) that are contained
in consumer and industrial products, are ultimately circulated globally due to the
products’ waste/recycling path. These global pollutant cycles are likely to pose
risks to humans and the environment, but for a final evaluation of the impacts, many
basic data are lacking.
This article analyzes the question “How can the outcome of the project
RISKCYCLE influence European legislation?” In fact, there are many possible
ways in which the outcomes of the project RISKCYCLE can influence EU
regulation.
First, the Ecodesign Directive is a possibility to implement more precautionary
approach against risks posed by hazardous chemicals.
The second possibility is the European waste legislation, which includes the
Restriction of Hazardous Substances Directive (RoHS). The RoHS Directive is
closely linked with the Waste Electrical and Electronic Equipment Directive
(WEEE) which sets collection, recycling, and recovery targets for electrical
goods and is part of a legislative initiative to solve the problem of toxic e-waste.
And third, REACH (regulation concerning the Registration, Evaluation,
Authorisation and Restriction of Chemicals), the European new chemicals legisla-
tion, has interrelation to the waste sector and therefore to the project.
RISKCYCLE and EU Legislation 139

2 Ecodesign Directive

2.1 Basics

The Ecodesign Directive is the regulation that sets standards for products (products,
goods) at EU level. Thus, for the RISKCYCLE issue, principle regulations could be
established for the pre-consumer phase, so that only those chemical additives may
be used that do not cause problems in a sustainable closed substance cycle.
Originally only energy consuming products were considered as part of the EU
Ecodesign Directive. The scope of the Directive was extended in 2009 to the range
of products that are related to energy consumption (such as windows, insulation).
The EU Commission may establish minimum standards to improve efficiency of
energy-related products. Although energy is the focus of the Directive, other kinds
of resource consumption are considered, too. This is illustrated by the evaluation
methodology MEEuP (Methodology for the Ecodesign of Energy-using Products),
which is basic for the implementation of the Ecodesign Directive [2]. Under the
heading MEErP (Methodology for the Ecodesign of Energy-related Products) this
method is actually passing an evaluation and completion process due to the
expansion of the scope of the Directive [3]. The Eco-Report 2011 is an Excel-
based pre-computation method that allows for products to be assessed in terms of
their resource efficiency [4]. From this it is clear which indicators are to be applied
in future implementations of the Ecodesign Directive.
The European Commission has adopted a formal working plan for the implemen-
tation of the Directive. The current working plan 2009–2011 sets out an indicative list
of products and product groups, which are processed successively and in the end are
also regulated (air-conditioning and ventilation systems; electric and fossil-fuelled
heating equipment; food-preparing equipment; industrial and laboratory furnaces and
ovens; machine tools; network, data processing, and data storing equipment;
refrigerating and freezing equipment; sound and imaging equipment; transformers;
water-using equipment) [5]. The new working plan 2012–2014 is in the vote [6].
The regulation of each type of product group is preceded by an expert study
(preparatory study), which is then scrutinized intensively in a stakeholder process.
How can the Ecodesign Directive be further developed to handle the
RISKCYCLE-topic? So far, pollution issues are involved in the context of product
evaluation and the derivation of product standards, but rather in the sense of LCA to
capture the energy side and the other relevant environmental indicators. The topic
of mercury in compact fluorescent lamps (CFL) has made it clear that pollution
issues can be quite important in the context of this Directive. However, relevant
limits for energy saving lamps were first set by a waste-related regulation, namely
the Annex of the WEEE Directive [7].
Currently (2012) there is an internal discussion within the Commission on the
evaluation of the Ecodesign Directive. One of the positions taken is to expand the
scope of the directive a second time to broaden its field of application. There are
some voices proposing to include the pollution issue in the context of setting
product standards. Decisions are expected in late 2012.
140 U. Lahl and B. Zeschmar-Lahl

2.2 Conclusion

The Ecodesign Directive can include selected pollutants in life cycle assessment
considerations (connected with the topic resource efficiency). This does, however,
not cover the topic RISKCYCLE.
At present it is unclear whether the scope of the Ecodesign Directive will be
extended a second time and whether the problem of pollutants in products will be
included. Since the focus of the policy will remain clearly on the energy aspect, it is
not expected that, even with expansion of the scope, the Ecodesign Directive can
make a relevant contribution to solving the problem highlighted in RISKCYCLE.

3 Waste Legislation

3.1 Basics

In the past, product-related standards in the European waste law were rare. This
changed with the triumphal success of everyday electronic gadgets and the associated
increase in e-scrap. The EC Directive 2002/96/EC – better known as the WEEE
directive – aimed to combat the increasing amount of e-waste from electrical and
electronic devices [8]. Goal is the avoidance, reduction, and environment-friendly
disposal of increasing amounts of electronic waste through extended producer
responsibility. This goal has been hindered by a number of pollutants that are
included in the devices (RISKCYCLE).
For this purpose, the WEEE Directive has been complemented with an addi-
tional directive that limits the use of certain pollutants in these products. The EC
Directive 2002/95/EC on the Restriction of the use of certain Hazardous Substances
in electrical and electronic equipment (RoHS Directive) ([7], recast 2011 [9])
restricts the use of the six harmful substances/substance families lead, mercury,
hexavalent chromium, polybrominated biphenyls (PBB), and polybrominated
diphenyl ethers (PBDE) to 0.1% and cadmium to 0.01% w/w per homogenous
material in equipment and components, but with several exemptions for a wide
range of applications (Annex III and IV).
In particular, the RoHS Directive has been proven in Europe. Those substances
are now banned from the products (below the limit values). In addition, the
international equipment manufacturers have switched their production, not limited
to Europe, but made for the world market. This in turn has led to the creation of laws
similar to the RoHS regulation in other regions of the world.

3.2 Conclusion

In the sector of electrical and electronic equipment, the RoHS Directive, as
explained, has successfully resulted in reduction of hazardous chemicals in line
with goals of the RISKCYCLE project and has reduced many problems. This raises
RISKCYCLE and EU Legislation 141

the question whether the RoHs Directive can offer a further contribution for solving
the problem. This would require an extension of the scope of the Directive in two
aspects:
• Expansion of product scope, including other products in addition to electrical
and electronic equipment
• Extension of the catalog of restricted substances (Annex II of Directive)
Article 6 of the RoHS Directive (recast 2011 [9]) says: “1. With a view to
achieving the objectives set out in Article 1 and taking account of the precautionary
principle, a review, based on a thorough assessment, and amendment of the list of
restricted substances in Annex II shall be considered by the Commission before 22
July 2014, and periodically thereafter on its own initiative or following the submis-
sion of a proposal by a Member State . . .”.
Thus, the door would be open for this extension. Whether it succeeds also to
extend the scope of the Directive to other RISKCYCLE-related products is doubt-
ful. No such advances are known.
Furthermore, the instrumentation of the RoHS Directive has to be considered in
this context. The Directive is targeting a clearly structured business sector with very
few clear substance bans (or more precisely: limits). For the regulated pollutants in
turn very unique risk considerations are possible. Without an extension of the
instrumentation to a more sophisticated control system, the complex (chemical)
process cannot be reproduced in other sectors.

4 REACH: The European Chemicals Legislation

REACH has now been in force for 5 years. REACH is setting the legal frame for the
chemical sector. But REACH also gave a task, which is to work off for more than 15
years: a “safety check” for all existing chemicals.
This “safety check” is in the first approach a check the responsible manufacturer
or importer has to do in his own responsibility. In a second approach, it is to some
extent also a check which is done by the competent authorities, especially the
European Chemicals Agency (ECHA) and the national authorities.
For this, the manufacturer and the importer have to register the chemicals they
are placing on the European market. The registration is mandatory for all chemicals
that are sold in a volume of more than 1 Mg/a. With the registration the manufac-
turer and the importer have to provide a special registration dossier. This dossier
should cover all necessary information to do the “safety check.” To be precise, the
structure of the dossier has to follow well-defined requirements, which will not be
explained in this article. More information is offered here [10, 11].
Meanwhile the first “tranche” of the registration is done for all chemicals with a
market volume of more than 1,000 Mg/a and for chemicals which have a high
concern out of hazardous reasons (e.g., carcinogenic, mutagenic, or toxic to repro-
duction (CMR)). By the REACH deadline of 30 November 2010 for the first tranche,
24,675 registration dossiers were submitted for 4,300 substances including nearly
142 U. Lahl and B. Zeschmar-Lahl

3,400 phase-in substances [12]. In the coming years the rest of the existing chemicals
have to be registered. Currently the evaluation of the dossiers takes place.
The REACH regulation states that after a 5-year period there should be an
evaluation of the regulation itself. First the commission has to give a report about
the lessons learned: “The Commission will launch a review which will consist of the
legally required reviews and reports: (a) the review of ECHA (Article 75.2), (b) the
review to assess whether or not to amend the scope of REACH in order to avoid
overlaps with other EU legislation (Article 138.6), and (c) a general report from the
experience acquired in the operation of the regulation (Article 117.4) including a
review of the requirements relating to registration of low tonnage substances
(Article 138(3)) and the information submitted by the Member States and ECHA
in their respective reports on the operation of REACH (Art.117(1)(2)(3)).” [13].
This evaluation is on the way. The different stakeholders have made their
proposals regarding what should be modified or supplemented. Our proposals like
improvement of transparency, installation of a positive list, and a household product
database (HPDB) have been published some weeks ago, including the topic REACH
and RISKCYCLE [14]. This article only covers the topic “RISKCYCLE,” but more
in depth.

5 REACH and RISKCYCLE

5.1 REACH Regulations on Waste

The RISKCYCLE project deals with chemicals, but with those beyond their actual
use phase, when they have entered the phase after end of service life, that means the
waste phase. But is this area not considered legally outside the scope of REACH
and more covered by waste legislation? The answer to this question is quite clear.
Without doubt REACH covers the waste period, too. Thus, REACH is also suitable,
in principle, to implement the findings of RISKCYCLE by legislation or regulation.
As Article 2(2) of REACH provides that “waste as defined in Directive 2006/12/
EC is not a substance, mixture or article within the meaning of Article 3 of this
Regulation,” REACH requirements for substances, mixtures, and articles do not
apply to waste. However, as soon as a material or a waste “ceases to be waste,” it
becomes instead a product in the eyes of the EU’s legislators and is falling under the
REACH regulation.

5.2 REACH Regulations on Recovered Materials

Waste fractions leaving the recycling process of waste as a recovered material have
to fulfill the obligations of the REACH regulation, but with certain privileges.
Article 2(7d) provides under certain conditions for an exemption from registration
(Title II), downstream user regulations (Title V), and evaluation (Title VI) [10]:
RISKCYCLE and EU Legislation 143

7. The following shall be exempted from Titles II, V and VI:
(d) substances, on their own, in preparations or in articles, which have been registered in
accordance with Title II and which are recovered in the Community if:
(i) the substance that results from the recovery process is the same as the substance that has
been registered in accordance with Title II; and
(ii) the information required by Articles 311 or 322 relating to the substance that has been
registered in accordance with Title II is available to the establishment undertaking the
recovery.

This means, if the recovered material is identical to a substance already
registered and if the information on hazardous properties is available, e.g., from
the safety data sheet, a registration is no longer mandatory.
But when does a material or a waste “cease to be waste?” The End-of-waste
status is specified in Article 6 of the revised Waste Framework Directive 2008/
98/EC:
1. Certain specified waste shall cease to be waste . . . when it has undergone a recovery,
including recycling, operation and complies with specific criteria to be developed in
accordance with the following conditions:
(a) the substance or object is commonly used for specific purposes;
(b) a market or demand exists for such a substance or object;
(c) the substance or object fulfills the technical requirements for the specific purposes and
meets the existing legislation and standards applicable to products; and
(d) the use of the substance or object will not lead to overall adverse environmental or
human health impacts.
The criteria shall include limit values for pollutants where necessary and shall take into
account any possible adverse environmental effects of the substance or object.
2. . . . End-of-waste specific criteria should be considered, among others, at least for
aggregates, paper, glass, metal, tyres and textiles.

ECHA points out that some materials currently considered as waste might in
future be considered to have “ceased to be waste” [15]. These materials will then be
out of the scope of waste legislation, and – if not covered by an exemption – will
potentially fall under REACH. Clarification of end-of-waste criteria is a matter for
waste legislation. In accordance with the general principle of subsidiarity of the
European Union law, and following the revised Waste Framework Directive,
Member States may decide case by case whether certain waste has “ceased to be
waste,” where end-of-waste criteria have not been set at Community level. Member
States have already worked for use of this regulation, like, e.g., the Waste Quality
Protocol in England, Wales, and Northern Ireland [16].
The Commission is working on establishing end-of-waste criteria for a number
of specific recyclable materials including metal scrap of copper, aluminum and
iron, waste paper, waste glass, compost, and plastics. Based on the results of
two frontrunner studies, ferrous scrap and aluminum scrap in 2010, the first

1
Requirements for Safety Data Sheets.
2
Duty to communicate information down the supply chain for substances on their own or in
preparations for which a safety data sheet is not required.
144 U. Lahl and B. Zeschmar-Lahl

End-of-Waste Regulation (333/2011/EC) has been adopted [17]. It applies to the
EU since 9 October 2011. Following JRC/SUSPROC, based on a second round of
technical studies on waste paper, copper and copper alloy scrap, as well as waste
glass (glass cullet), regulations for end of waste on these materials are currently
being prepared in comitology. Further studies are performed on biodegradable
waste and waste plastics, and the development of end-of-waste criteria on
aggregates and waste-derived fuels is in discussion [18].

5.3 REACH Regulations on Waste Life Cycle Stage of Substances

REACH requirements for substances, mixtures, and articles do not apply to waste
itself. “Nevertheless manufacturers and importers of substances, downstream users
and potentially recipients of articles have a number of duties under REACH related
to substances in waste. Waste-related information must be included in the registra-
tion dossier for all substances, including those for which no CSR and/or SDS3 is
required (<10 t/a) or which are not classified as dangerous.” [19].
With regard to the outcome of RISKCYCLE, the obligations for products
containing hazardous substances are of great concern, as a risk characterization is
mandatory. Following Article 14(4) of REACH, the chemical safety assessment
(CSA) shall include the following additional steps if the substance meets the criteria
for classification as dangerous in accordance with Directive 67/548/EEC or is
assessed to be a PBT (persistent, bioaccumulative and toxic) or vPvB (very
persistent and very bioaccumulative) substance:
(a) Exposure assessment including the generation of exposure scenario(s) (or the
identification of relevant use and exposure categories if appropriate) and expo-
sure estimation
(b) Risk characterization
For these substances, “the waste life stage of the substance needs to be covered
by suitable exposure scenarios, the corresponding exposure estimation and the
related risk characterisation. The conditions ensuring control of risk in the waste
life stage of the substance need to be documented in the chemical safety report
(CSR) and also communicated in the supply chain by means of the extended safety
data sheet.” [19].
Article 3(37) of REACH defines exposure scenarios as “the set of conditions,
including operational conditions and risk management measures, that describe how
the substance is manufactured or used during its life-cycle and how the manufac-
turer or importer controls, or recommends downstream users to control, exposures
of humans and the environment [. . .]”.

3
Chemical safety report and/or safety data sheet.
RISKCYCLE and EU Legislation 145

The CSA has to cover the whole life cycle of the substance in the exposure
assessment. Following Annex I paragraph 5.2.2 of REACH the waste stage is to be
assessed where relevant: “The emission estimation shall consider the emissions
during all relevant parts of the life-cycle of the substance resulting from the
manufacture and each of the identified uses. The life-cycle stages resulting from
the manufacture of the substance cover, where relevant, the waste stage. The life-
cycle stages resulting from identified uses cover, where relevant, the service-life
of articles and the waste stage. The emission estimation shall be performed under
the assumption that the risk management measures and operational conditions
described in the exposure scenario have been implemented.” Furthermore, follow-
ing Annex I paragraph 5.1.1 of REACH, the Risk Management Measures of an
Exposure Scenario shall in particular include, where relevant, a description of “the
waste management measures to reduce or avoid exposure of humans and the
environment to the substance during waste disposal and/or recycling.”

5.4 Risk Management Measures of Exposure Scenarios

ECHA’s Guidance on information requirements and CSA, Chapter R.18, gives
detailed information about exposure scenario building and environmental release
estimation for the waste life stage.

Concise Guidance In Depth Guidance

A: Introduction
R.2-R.7: Information Requirements

R.8-R.10: Dose- or Concentration-
B: Hazard Assessment
Response Characterisation

C: PBT and vPvB Assessment R.11: PBT/vPvB Assessment

R.12: Description of Uses

D: Exposure Assessment R.13: Concitions of Use (RMM,OC)

R.14-18: Exposure Estimation

E: Risk Characterisation R.19: Uncertainty Assessment

F: Chemical Safety Report
R.20: Explanation of Terms

G: Extension of the SDS

Fig. 1 Structure of the Guidance [20]
146 U. Lahl and B. Zeschmar-Lahl

This Guidance is part of a series of guidance documents that aim to help all
stakeholders with their preparation for fulfilling their obligations under the REACH
Regulation. The Guidance consists of two major parts: Concise guidance (Part A to G)
and supporting reference guidance (Chapters R.2 to R.20) (see Fig. 1).
Figure 2 illustrates the workflow and location in the guidance of the relevant
information for Chapter R.18 [19].
Registrants can choose which kind of approach they want to use for the quanti-
tative exposure assessment for the waste life stage. The guidance contains examples
for calculation of releases at local and at regional scale, as they are driven by the
operational conditions and risk management measures relevant for the different
uses. The Assessment of distribution and fate of the substance in the environment
mainly driven by substance properties, once the substance has been released to the
environment, is only addressed in Guidance R.16 [21], as this step is independent of
the life cycle stage. The guidance contains in addition workflows for the generic and
the specific approach.
In the following, the approach for the releases at regional scale is described.
Figure 3 provides an overview of waste generation during the life cycle of a
substance and examples of related possible sources of information.
For calculation of the waste life stage’s contribution to the release of the
substance at regional scale, a standard model of a European region with about 20
million inhabitants and defined parameters (e.g., size, volume of water, soil,
sediments and biota, etc.) is used; details are given in Chapter R.16: Environmental
Exposure Estimation [21].
In order to calculate the regional releases from waste treatment in the default conservative
approach (Tier 1), again two cases are distinguished: i) Waste from manufacture and
industrial uses and ii) waste from dispersive uses and article service life. The fraction of
the registrant’s total amount per use assumed to be treated in the region (Qmax,regional) is
different for the two cases: For manufacture and industrial uses the total use and related
waste amount is assumed to occur in one region. For dispersive use and article service life,
it is assumed that 10% of the registrant’s total volume occurs in the region for use and
related waste treatment [19].

At regional scale all the releases occurring at the different life cycle stages are
summed up. Figure 4 shows the input parameters and the results of the release
assessment at regional scale. The outputs are the annual amounts of substance
released to the different environmental compartments (regional air, regional
water, regional soil).
As an alternative to these calculations, the registrant may choose to make a
generic release estimate. Here, conservative default values are used for identifying
waste amounts and fractions entering into the three main waste streams. “Further-
more, generic exposure scenarios can be selected containing default release factors
and assumptions on implemented risk management in the processes.” [19].
Figure 5 shows the workflow for a generic approach. “In order to simplify and
structure the exposure assessment of the waste stage, the current assessment
approach distinguishes three main waste streams, each of which is connected
RISKCYCLE and EU Legislation 147

Characterisation of waste
streams
R.18.2

Waste sources
(R.18.2.1)

Waste destinations
(R.18.2.2)

Relevance of waste stage
(R.18.2.3)

Approach to exposure
assessment
Tier 1
(R.18.3)

Release at local scale
(R.18.3.1)

Release at regional scale
(R.18.3.2)
Information source in the guidance
Generic workflows Required Necessary
(18.3.3-4) parameters information
Default assessment Refinement

Use conditions
Fwaste Appendix 18-4 Appendix 18-4
Exposure scenario (fraction becoming
building waste) Waste destination
and release estimation

Qmax Use quantity
R.18.4 (max amount
treated d/y at site) Dispersiveness of
waste treatment Appendix 18-4
processes
Appendix 18-3
Waste treatment (distributions
RF process Appendix 18-2 schemes)
Exposure assessment and (release factors) Appendix 18-5
RC (refinement options)
R.18.5

Risk
controlled?

Substance - specific risks

R.18.6

Documentation and
communication
R.18.7

Fig. 2 Chapter R.18: illustration of the workflow and location in the guidance of the relevant
information [19]
148 U. Lahl and B. Zeschmar-Lahl

Fig. 3 Types of waste generated along the life cycle of a substance [19]

Fig. 4 Determinants and results of regional release estimation for the waste stage [19]
RISKCYCLE and EU Legislation 149

Fig. 5 Workflow for generic approach [19]

with the most typical waste treatment processes: municipal waste (MW), recycling
waste (RW) and hazardous wastes (HW) (see Section R.18.2.2).” [19]

5.5 Results

The research project RISKCYCLE has compiled relevant information highlighting
the risks of the chemicals that are recycled in regional and global systems. Many of
these risks are being provoked due to the fact that manufacturers of chemicals or
other items did not make efforts to pursue the item and its chemicals along its way
in the product cycle up till the waste stage. The waste stage is not being appropri-
ately taken into consideration in life cycle assessments.
It has been approximately 5 years since the European law on chemicals REACH
came into force. It was implemented to audit the risks of all chemicals on the market
by their sales volume and hazardousness. The essential aim of this security check is
to determine so-called “exposure scenarios,” which facilitates the assessment of the
occurrence of unacceptable or dangerous exposure created by the evaluated chemi-
cal. If these risks are identified, measures are to be taken to reduce the exposure by
restrictions on usage or by issuing a ban.
150 U. Lahl and B. Zeschmar-Lahl

This information is to be submitted to the authorized ECHA for the purpose of
substance registrations (details see above in clause 3.4). The essential information
should be recorded in the factsheet (SDS) of each chemical including exposure
scenarios in case they are substantial. This article describes the importance of the
waste stage in the drafting of exposure scenarios. The waste phase is to be included
in the calculation of exposure. As part of the implementation of REACH, guidance
documents were developed with detailed recommendations which describe how
this is to be done. Important aspects of this procedure are explained above.
As a consequence of the implementation of REACH, many problems described
in the RISKCYCLE project would become relevant. These described gaps in
knowledge are in parts to be extracted from the registration dossiers. The informa-
tion will be gained depending on the processing status of REACH registrations.
Currently, only the so-called first tranche of hazardous chemicals and also
chemicals with a market volume of more than 1,000 Mg/a have been registered.
Further tranches will follow the next few years.
The analysis of the currently available registration dossiers indicates that they
have some serious shortcomings. It is yet unknown whether the mandatory regis-
tration of the waste stage in the dossier has been sufficient.

6 Prospect

All three routes (Ecodesign, RoHS, and REACH) are feasible for influencing
European legislation by the outcome of the project. There is one argument that
indicates REACH is the most promising route: the outcome of RISKCYCLE is a
“complex chemical matter.” This is the original domain of REACH!
The instrumentation of REACH is differentiated and targeted to this complex
regulatory field. And the waste phase, as shown, is explicitly subject to exposure
scenario building, which in turn is the basis for substance evaluation and the
resulting management measures to be derived.
For this it must be questioned whether the stipulations in REACH and in the
relevant guidance documents are sufficient to solve the explained problem of
RISKCYCLE. The represented stipulations for the determination of exposure
scenarios in the waste stage are, in our view, sufficiently detailed as well as
extensively and professionally prepared to solve the problems of RISKCYCLE
through REACH implementation.
Problematic is the implementation of REACH within the personal responsibility
of the registrant for his registration dossier. Our thesis is that the quality problems
that are currently often deplored at the main registration pathways are likely to
become even more serious on “side roads.” And from the perspective of a chemical
manufacturer the waste stage is commonly seen as such a side road. To solve this,
we have three suggestions:
1. The RISKCYCLE issue should be explicitly noted in the regulatory text to raise
awareness among the registrants of this topic.
RISKCYCLE and EU Legislation 151

2. The ongoing analysis of registration dossiers should be considered and
performed with sensitivity to the waste stage. This should also be done for the
selection of substances of very high concern (SVHC, candidate list). For this
purpose this task should be designated to the ECHA.
3. A previous proposal given in the process of designing REACH could be helpful:
the introduction of quality assurance mechanisms in REACH regulation. This
proposal could not be implemented due to the lack of majority during the
political decision process on structuring REACH. But today’s situation shows
that such a mechanism is needed. Quality assurance mechanisms could be
arranged privately. Before a registration is submitted the file could be proofed
by an independent expert for completeness and defined content requirements.
Without such an examination a registration would be incomplete.
The auditors themselves may be obliged to undergo an approval process for
independent and high quality work. Since the amendments to REACH are currently
on the European political agenda, 2012 would be a convenient time to introduce
these three proposals.

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Part II
Case Studies
Two Sides of One Coin: Relations Between
Hazardous Substances and Valuable Resources

Henning Friege

Abstract Many hazardous substances of today had been looked at as valuable
chemicals some decades ago. At present, management especially in the case
of scarce, non-renewable resources is of growing importance. The experiences
collected with the management of contaminants might be helpful also for valuable
resources. This is demonstrated using two well-documented examples, Cd and
PCBs. Pt serves as a counterexample to prove if the DPSIR method can be applied
to contaminants and resources without fundamental changes. Some of the
countermeasures introduced to control environmental contaminants may also be
applied to save non-renewable resources.

Keywords Cadmium, DPSIR method, Hazardous waste, PCBs, Platinum,
Resources

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
2 Outline of the Problem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
3 Cadmium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
4 Polychlorinated Biphenyls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
5 The DPSIR Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166

H. Friege (*)
AWISTA Gesellschaft für Abfallwirtschaft und Stadtreinigung mbH, Höherweg 100,
40233 Düsseldorf, Germany
e-mail: hfriege@awista.de

B. Bilitewski et al. (eds.), Global Risk-Based Management of Chemical Additives II: 155
Risk-Based Assessment and Management Strategies, Hdb Env Chem (2013) 23: 155–170,
DOI 10.1007/698_2012_188, # Springer-Verlag Berlin Heidelberg 2012,
Published online: 31 August 2012
156 H. Friege

1 Introduction

Resource conservation and resource recovery are an issue of growing importance
on the agenda of international policy [1]. With respect to the basic rules of
sustainable management of substance chains, “the consumption of non-renewable
resources should be limited to levels at which they can either be replaced by
physically or functionally equivalent renewable resources or at which consumption
can be offset by increasing the productivity of renewable or non-renewable
resources” [2, 3]. Societies all over the world are far away from complying with
this rule. Increasing amounts of non-renewable resources may lead to regional or
worldwide scarcities already indicated by a steep increase of the prices for some
specific resources. This is especially true for some rare metals. Many of these
elements have never been used in industrial scale before the last decades of the
twentieth century. Now, the demand is rising rapidly for industrial use mostly for
very interesting technologies and private consumption mostly in electric and
electronic devices. These metals are either found in extremely low concentrations
in minerals or are mixed up with other elements with similar physical and chemical
properties. Therefore, separation processes are difficult and energy consuming.
Especially rare earth metals and the elements of the platinum group (PGM –
platinum group metals) are only mined in few areas in the world. Therefore, the
supply with these elements is endangered by technical, economical and political
obstacles. The European Commission started strategic work on resources [4, 5]
focussing on
– A globally free market for non-renewable resources
– More extraction of minerals in Europe
– Higher efficiency in the use of resources and recycling

2 Outline of the Problem

Waste management is expected to contribute to resource conservation by the
recycling of used goods. There are a lot of experiences with the recycling of
resources from used goods (paper, cardboard, glass bottles, plastic packaging. . .)
made of renewable as well as of non-renewable resources. All these goods have a
more or less homogeneous composition based on easily available materials. The
recovery of scarce resources from waste turns out to be far more difficult. This may
be easily explained by the general dilemmas of waste management [6, 7], i.e.
– The entropy dilemma, i.e. small concentrations of valuable substances in used
products leading to complicated and energy consuming recovery processes
– The dissipation dilemma, i.e. high dissipation of products being an obstacle for
collection
Two Sides of One Coin: Relations Between Hazardous Substances and Valuable. . . 157

– The double role of waste and valuables, i.e. contamination of used items
containing valuable resources by dangerous compounds
– Different opportunity costs for waste disposal for people with different inducing
informal collection activities
– A time lag between the production of a good and its final fate as waste leading to
lack of specific secondary resources during the useful life of the items
Quite a number of useful chemicals introduced some decades ago later turned
out to be hazardous and have therefore been substituted by other substances. Very
often, the following phases are observed:
– Placing the substance on the market for few applications
– More and more application fields
– Hazardous properties published; public pressure against further use
– Substitution of the substance in question by less hazardous alternatives
– Adaption of concentration limits (emission, food. . .) in case of persistent
compounds
– Ban of the substance often with a transition period depending on the application
area
– Phasing out of products containing the substance in question (going to the waste
bin)
– Special treatment requirements for waste including the hazardous substance
Especially in the case of solid substances, waste management is responsible for
the clean-up of the technosphere, i.e. collection and disposal of the chemical in
question. With respect to hazardous compounds in used goods, tools have been
developed to phase out these goods for special recycling procedures or safe
disposal.
The experience collected with hazardous compounds in waste shall be compared
with the problem of scarce resources in waste using well-known examples. The
comparison must be extended to other phases of the “life cycle” of products,
because waste management is only a part of substance chain management. The
instruments used for the management of hazardous chemicals will be analyzed
using some examples to answer the question if they could also be useful for scarce
resources.

3 Cadmium

Cadmium (Cd) has a number of interesting technical characteristics. Plating with
Cd yields high protection against corrosion also in saline environment. CdS, CdO,
CdSe, and mixed salts are thermally stable pigments showing bright and luminous
colours. Cd stearate turned out to be an excellent stabilizer for PVC against sun
light. Ni/Cd is an electric cell with a battery voltage of 1.2 V. Recently, CdTe has
been introduced as semi-conducting material in photovoltaic (PV) thin layer cells.
158 H. Friege

In the twentieth century, Cd was declared to be an element of strategic importance
by the U.S. government (cited from [8]) due to its importance for plating (marine
applications) and accumulators. The atomic structure of Cd resembles zinc (Zn) and
also calcium (Ca). Zn ores contain Cd in low concentrations. Therefore, Cd is
normally obtained as a by-product of Zn smelting, but is also found in the dust of
copper and lead smelters. Small concentrations of Cd are found in phosphate
minerals depending on the origin (Morocco/Sahara ~60–120 ppm, North America,
Russia ~20 ppm with respect to P2O5 [9]). Traces of Cd are also found in coal and
oil thus leading to emissions from treatment of fuel and power stations.
From the 1950s on, there were findings that Cd is toxic for humans in low
concentrations. The important target organs are kidney and liver, Cd accumulating
mainly in the adrenal cortex. Its half-life in humans ranges between 10 and 30 years.
Cd and CdO are assessed to be potent carcinogens. Some years ago, the tolerable
weekly intake (TWI) has been decreased by a European group of experts to 2.5 mg/
kg b.w. (body weight) [10]. The mean intake of Cd by German citizens is about
1.5 mg/kg b.w.; in special groups like vegetarians with high food consumption or
smokers the TWI might be exceeded [11].
The production peak (world wide production ~20,000 Mg) was attained in the
1980s. In 2004, the overall production in Europe was about 4,600 Mg, nearly half of
the production volume being exported [12]. The production figures mean isolation
of Cd as a pure metal. Besides that, Cd is found as an impurity in commercial Zn
products and as part of the waste from Zn smelters.
To address the root of the problem, chemical policy focuses on the substance
itself: With respect to the inherent hazards of Cd-containing products, all highly
entropic applications like pigments, stabilizers, and plating have been banned.
Following the Battery directive [13], more than 0.002% Cd (w/w) in accumulators
is prohibited with the exception of medical appliances, military use, alarm systems
and cordless electric tools. In electric and electronic devices, Cd concentrations
may not exceed 0.01% as stipulated by the RoHS Directive [14, 15]. This is not
valid for PV cells: the amount of CdTe used in this field is increasing enormously.
Today, CdTe semiconductors in thin layers and Ni/Cd accumulators are the most
important application areas for Cd in Europe, the first increasing, the latter decreas-
ing. The concentration of Cd in Zn and products containing Zn is restricted by
quality requirements defined in the European standards EN 1179 (for refined Zinc
metal) and EN 10240 (for Zinc coatings of steel, e.g. pipes). To reduce emissions
from production and recycling, limit values have been set up for waste water,
exhaust gas, and sludge from waste water purification to be used as fertilizer.
There are also threshold values for environmental compartments like surface
water. Cd concentrations in food are also strictly limited to protect the consumers,
who are exposed especially by the consumption of liver, kidney, mushrooms and
bread. As to the remaining appliances, recovery after use is important:
– Ni/Cd accumulators are collected with respect to the Battery Directive, the
collection target being 25% with respect to the amount of batteries sold. As to
Germany, in 2009 1,141 Mg Ni/Cd accumulators were collected and 802 Mg
Two Sides of One Coin: Relations Between Hazardous Substances and Valuable. . . 159

sold [16]. As the time of sale is not known, recovery quota cannot be calculated
from these figures. In 2004, the relation between used Ni/Cd accumulators
collected and Ni/Cd accumulators sold was about one third [17]. With respect
to all types of batteries and accumulators sold, the European collection target
will be enhanced up to 35% (starting in 2012). In Germany, the collection has
reached 44%. It is reasonable to assume that about 50% or more of Ni/Cd
accumulators are not collected separately. A compulsory deposit for Ni/Cd
batteries has therefore been discussed to enforce the return.
– CdTe cells have to be collected after use following the latest revision of the
WEEE Directive, the collection target corresponding to other e-waste [18]. Until
2016, the yearly collection target of 4 kg per inhabitant remains valid. Starting in
2016, the collection target for used electrical and electronic equipment will
reach 45% (65% after 2019) of the products sold with respect to the average
of three foregoing years. Considering the long lifetime of PV cells, this regula-
tion is not practical without further provisions. As PV cells have been integrated
into the WEEE regulation [18], producers are enforced to give a take-back
guarantee independent of the average useful life of the devices. Some producers
already started the setup of a voluntary take-back system before the amendment
to avoid a legally binding rule [19].
Complete balances based on the analysis of material streams containing Cd in
relevant amounts have not been published in the literature in the last years with few
exceptions which are based on data from the beginning of the century [12, 20].
Therefore, the actual mass flow of Cd into the technosphere and its further fate in
the environment after use cannot be described quantitatively. The overall emissions
from German point sources sum up to about 2 Mg in the year 2009 [21] being very
small as compared to the Cd flows from products. Among the point sources, power
stations and steel mills are remarkable where Cd is emitted as a contaminant from
fuel or from scrap. Part of the emissions originates from recycling of scrap
including high levels of non-ferrous metals like Cu, Zn, Pb where Cd is an
accompanying element. According to the register [21], there is no WtE plant
among the important point sources.
Dissipated products containing Cd like pigments, stabilizers and plated
compounds will be found in normal waste. As outlined above, this might be also
valid for ~50% of the batteries. The concentration of Cd in municipal waste ranges
from 6.1 (rural areas) to 11.1 (cities) g/Mg dry waste [22]. This relatively large
mass flow of approximately >100 Mg is split up by disposal in MWIs, the amount
of Cd leaving the stack as flue gas is <1% as compared to the input [23, 24]. Normal
MWIs with a mean input of 6,700 mg Cd per Mg waste have very low emissions of
about 4.6 mg per Mg input [25]. Cd retained in flue ash is going to underground
mines, the other part remains in bottom ash.
Long-lasting measurements of the environmental background contamination
(particulate matter and air in areas far away from cities and industry) and analytical
data of food and biota prove that the transport into the environment is slowly
decreasing. The actual emissions in Europe decreased from 500 Mg/year (1990)
160 H. Friege

to about 250–280 Mg/year (2005–2008) [26], diffuse sources becoming more and
more important. In areas far away from remaining point sources, resuspended
particles add up to about 50% of the immission. Having these trends in mind, future
Cd immissions may remain constant.
The view at Cadmium changed with time starting from a valuable resource and
ending up as a toxic element with a limited number of applications not substituted
by alternative products. The decontamination of the technosphere works to a certain
extent. Due to the character of Cd as trace contamination of phosphate fertilizers
and of Zn ores and fossil fuels, there is no final solution for the environmental
contamination. Due to the restrictions issued in many countries, there is reason to
fear that Cd could end up in unknown material streams. From an analysis of the
refining of Zn ores in 2002, it has been concluded that about one quarter of Cd
generated as by-product (~7,000–8,000 Mg) could not be found either in the
products analyzed or in the emissions from the process [27].

4 Polychlorinated Biphenyls

The production of polychlorinated biphenyls (PCBs) started in 1930 driven by the
need for hardly inflammable isolation material for capacitors and transformers.
PCBs were also introduced as heat exchanger fluids because of its good thermal
conductivity. Its stability against heat led to application in mines as hydraulic fluids.
Due to recognition about toxic and cancerogenic properties starting with the Yusho
disease in 1968 and scientific findings about the enormous accumulation of PCBs in
marine sediments and biota, pressure against this group of substances sharply
increased. Therefore, the use and/or the production of PCBs were banned in
industrialized countries, first in Japan. PCBs number among the persistent organic
pollutants banned world wide (POP convention). Today, the PCB contamination of
German citizens by food is in the range of the TWI, in special groups also above the
TWI [28]. The body burdens decrease slowly [29].
Some typical areas of former use are presented in Table 1 with an assessment of
the problems coming up with the separation of used products containing PCBs. The
overall production was about 1.5 Mio Mg until the end of the eighties. Many
production lines ceased already until 1980. In Europe, PCBs were banned first for
“open” [30], then for “closed” applications [31]. But many of the closed
applications turned out to be open in reality, as has been demonstrated for hydraulic
fluids used in German coal mines, where up to two third of the annual consumption
of PCBs were lost [32].
About one third of the overall production was applied in buildings used as
additives to dyes and joint sealers. Normally, the use of PCBs in the materials is
not (more) known to the inhabitants or users of the houses. Only in the case of
secondary contamination of ambient air or food detected by chance or by system-
atic search, those buildings were decontaminated. Spreading of PCBs into the
environment was accelerated by mixing of used hydraulic or heat exchanger fluids
Two Sides of One Coin: Relations Between Hazardous Substances and Valuable. . . 161

Table 1 Some important applications of PCBs in relation to waste management
Type of PCB Type of Intended way/normal Separation from other
used application way of disposal items
Isolating agent in Cl  54% “Closed” Special waste Easy
transformers
Hydraulic fluid in Tri- and “Closed” Special waste/waste Difficult in underground
mining Tetra-CBs water from mine mines
equipment draining
Isolating agent in Cl  42% “Closed” Waste from electric Possible in state-of-the-
small and electronic art sorting plants
capacitors equipment/
household waste
Additive to joint All technical “Open” Hazardous waste/ Possible in state-of-the
sealer mixtures mixed art dismantling
construction waste processes

with waste mineral oil which was refined and used as marine diesel. To stop this
contamination pathway, oil with more than 50 mg/kg PCBs has to be treated as PCB
waste [33].
In the case of transformers and industrial hydraulic equipment, PCBs were used
together with steel, copper and other valuable materials. An exchange of PCB
containing equipment at once short after the PCB ban
• Would have led to stranded investments
• Would have overloaded the disposal capacities available at that time
Therefore, closed-loop appliances, i.e. transformers and large capacitors, with
PCB concentrations over 50 mg/kg could be operated further until 2000, in case of a
special exemption also until 2010. These devices could be easily identified by a
compulsory label. It is assumed that an overwhelming percentage of these items
were separately disposed. Instead of disposal of the complete devices, isolating
fluids can be exchanged by other chemicals. The complete cleaning of conta-
minated transformers is somewhat difficult and should be done very carefully to
avoid PCB impurities after refilling with other liquids [34]. These impurities
originate from PCB oil adsorbed on copper windings and on the walls as a sort of
tailing which leads to increasing concentrations in the new isolation fluid. There-
fore, most of the transformers and large condensers were stored in salt mines as
complete devices. Due to increasing copper prices, a lot of transformers already
disposed under ground have been brought back to treatment plants in the last years.
If the contaminated fluids are completely removed in a cleaning process, this might
be a good method to save resources. But again, the cleaning procedure turned out to
be unsafe. A company specialized on this treatment was closed down in 2011
because of remarkable pollution of its workers and contamination of the facility [35].
Small capacitors containing PCBs and “electrolyte capacitors containing
substances of concern” must be separated in sorting plants according to the
WEEE Directive [36]. These capacitors with a unit weight between 100 and
162 H. Friege

300 g (a third of this being PCBs) [37] have been used until the end of the 1970s,
may be also later (imported domestic appliances). From a technical point of view,
more than 95% of all PCBs in electronic waste can be separated by the first step in a
sorting plant [38]. In a report of the German government, it is assumed that about
3.5 Mg capacitors contaminated with PCBs were separated and disposed in 2008 in
sorting plants [39]. In some e-scrap sorting facilities, PCB contaminations were
detected [40, 41] probably due to accidentally destroyed capacitors.
It is assumed that most small items containing PCBs, sealers, dyes, etc. have
been disposed with household or construction waste. Due to numerous dissipative
applications, on the one hand, and high persistence of PCBs, on the other hand, the
contaminations will last for further decades.

5 The DPSIR Approach

The most important measures introduced to avoid spreading of Cd and/or PCBs into
the environment may be summed up as follows:
– The ban of applications being open to the environment
– The prohibition of mixing up the contaminants with other chemicals
– The introduction of strict emission limits for production and disposal facilities
– The definition of concentrations for waste (in the case of PCBs) to be kept
separately
– The introduction of quality levels (e.g. in the case of Cd/Zn and for used oils)
– The limitation of transfer of the contaminants via sewage sludge used as
fertilizer
Limit values for food and fodder do not decrease the environmental burden.
Indeed, regulations of this type are a signal for the public enforcing the producers to
avoid contaminations in the chain of food production. Thus, the food industry is
acting as a steward influencing other industries: the pressure against unsafe man-
agement of contaminated by-products and waste increases. The labelling of large
devices including the contaminant serves as a caution signal leading to safe
handling of these devices to avoid accidents.
Experiences of this type are the basis of the DPSIR (“driving forces – pressure –
state – impact – response”) approach (Fig. 1), which has been introduced in
environmental policy as a link between ecological problems and economic and
social responses [43].
The examples reported above may be described in terms of the DPSIR frame-
work. Production and use of Cd or PCBs, respectively, are driving forces, whereas
the pressure has grown by emissions from production, waste disposal and particu-
larly from dissipative use in open systems (Cd: erosion of plating material or
pigments. . ., PCBs: evaporation from sealers. . .). Concentrations of the substances
in question analyzed in environmental compartments represent the state of the
Two Sides of One Coin: Relations Between Hazardous Substances and Valuable. . . 163

Drivers Responses

Causes Policies and targets

Pressures Impact

Pollutants Health, ecosystems,
materials
State

Quality

Fig. 1 The DPSIR scheme [42]

contamination. The burden of man and biota as well as harmful effects may be
taken as impacts caused by environmental pollution. All measures taken to decrease
the emissions of these substances, to recall products containing Cd or PCBs or to
reduce environmental contamination are interpreted as responses relating either to
direct impacts or to pressures or to the source of the problem, i.e. the driving forces
mentioned. Actions taken against Cd and PCBs as well as the specific objectives are
summarized in Table 2.
It is obvious that the driving forces causing the widespread use of a substance do
not change, when the substance in question turns out to be hazardous. To look
deeper into the potential comparability between valuable and hazardous
compounds, Platinum (Pt) may serve as an example. Mining of Pt is energy
consuming and causes enormous heaps of rock. The overall consumption world-
wide is about 200 Mg/year. (For a detailed material flow analysis, see [44] and the
literature cited therein.) In contrary to contaminants, the “impact” mainly results
from the scarcity of Pt. Very similar to the contaminants presented here, “pressure”
results also from dissipative uses leading to significant losses [45]. Increasing Pt
concentrations are found in soil in the vicinity of highways caused by emissions
from catalysts (“state”). Due to its high adsorption to soil, the mobility of Pt is low
as compared to many other metals. Organometallic molecules with Pt acting as
central element are found in waste water indicating considerable risk because of the
physiological effects of cis Pt complexes used as anticancer drugs. (For more
details see [45] and literature cited therein.) So, we can realize that “pressure”,
“state”, and “impact” for a valuable resource resemble the situation found for
hazardous substances. In the case of Pt, there is a flowing transition from “valuable”
to “hazardous” characteristics. Pt is therefore referred to as a “green polluter” [44]
or as a “Janus faced” element [45]. In the case of valuable resources widely used,
the high anthropogenic material flow represents the most important pressure driven
by production and consumption. Therefore one might differ between system-turn-
over-based indicators and impact-based indicators [44], the first relating to the input
164 H. Friege

Table 2 Experiences with Cd and PCBs compared with Pt in the framework of the DPSIR
approach
Comparison between
hazardous and
Cd PCBs Pt valuable substances
D Needed for economically +++ (+++) +++ Comparable
important application fields
D By-product from the synthesis of +++ + – Different
other substances or
contamination of a valuable
product
P Emissions of the substance from (+++) (+) Not investigated for Pt
production, processing,
recycling
P Application areas open to the ++ (++) ++ Comparable
environment or dissipative use
P High dispersion in the environment +++ +++ ++ Comparable
and highly accumulative
P Huge amount used (++) (+++) +++ Comparable
S Significant concentrations in +++ +++ + Partially comparable
samples from the environment
S Dispersion of a toxic substance +++ +++ + Pt: this depends on the
molecular
structure
S Anthropogenic production +++ +++ +++ Comparable
significant as compared to
geogenic flow
S Contamination of sinks (soil, +++ +++ + Partially comparable
sediment, atmosphere. . .)
I Contamination of food +++ ++ + Partially comparable
I Impacts on man +++ +++ Different by today’s
knowledge
I Impacts on other biota +++ +++ Pt: Not investigated
I Impacts on environmental systems + + Pt: Not investigated
I Scarce resource – NR ++ Completely different
from today’s view
I Obstacle for recovery of other +++ ++ NR Different
valuable resources
R Emission limits for the substance +++ + Different
from production and recycling
processes
R Limit values for food and feed +++ +++ NR Different
R Limit values for workplaces ++ ++ NR Different
R Substitution and/or closed loops +++ +++ ++ Comparable
for some products
R Ban for some/all applications + +++ Matter of policy
R Special methods for disposal ++ ++ +++ Comparable
and/or recovery
Explanation of the table: +++ very important, ++ important, + less important, – not valid.
D Driving forces, P Pressures, S State, I Impact, R Response, NR not relevant for this example.
Data in brackets refer to former use or emissions
Two Sides of One Coin: Relations Between Hazardous Substances and Valuable. . . 165

in the technosphere, the latter relating to the output into the environment. In the case
of Pt, we can indentify both. The view at Cd – see above – has changed from input
problems (scarcity) to output problems (environment) as impact.
The cases of Cd, PCBs, and Pt are compared in Table 2 following the empirical
DPSIR approach. Considering many similarities and some differences between
valuable and hazardous compounds, it is interesting to look for common
“responses”. As to the life cycle, substitution is a big issue for scarce as well as
for hazardous materials. In the case of hazardous substances, substitution is mostly
driven by legal issues, i.e. prohibition of certain appliances. In the case of scarce
resources, substitution is normally driven by the market. For many scarce metals,
signals indicating shortage in the long run may come too late to avoid wasting non-
renewable resources. The demand for rare metals needed for “green technologies”
is increasing continuously sometimes doubling within a few years (see for example
[46, 47]). It is therefore reasonable to enforce the substitution of these resources,
especially in the case of dissipative and/or open uses as it is found for Pt.
In the time lag between placing of a chemical on the market and regulations after
scientific findings about potentially hazardous properties, the chemical is spread out
in numerous application areas. In this case, waste management has the role of a
vacuum cleaner for the technosphere. In the case of a scarce resource, the situation
is very similar. Considering waste management as part of the “response”, both
groups might be managed in a similar way, i.e. separate collection of devices which
include hazardous or scarce substances also as a minor component. It is therefore
useful to establish regulations fitted to the type of waste in question. From the
collection, recycling, and disposal of waste from electric and electronic devices we
have learned that the difficulties are comparable for waste containing valuable
resources and hazardous compounds, respectively [48]. There is one important
exception: If the prices of the resource in question are high and only little efforts
are needed for the separation from normal waste, the informal sector will start
cherry picking thus disturbing public initiatives. The introduction of take-back
systems well known for batteries which are enforced by deposits could be a solution
for the collection of dissipated devices containing small amounts of scarce
materials.

6 Conclusions

From an empirical evaluation of the tools used to minimize the emissions, the
environmental contamination, and the exposure of man by hazardous chemicals one
may conclude that the following strategies could also be applied to save scarce
resources:
• The prohibition of use in dissipative application fields is the most important step
to reduce the distribution in the technosphere and to minimize the spread into the
environment.
166 H. Friege

• The concentrations of hazardous substances in waste are often limited with
respect to different disposal methods. This could also be discussed for valuable
resources to avoid mixing up of products containing the resource with other
waste items. If this dilution cannot be avoided, disposal in landfills or reuse as
part of construction material will lead to non-retrievable losses.
• Compulsory return especially of devices used commercially is very helpful for
the recovery of hazardous materials as well as goods with valuable resources. In
the latter case, economic incentives are needed as well.
• Strict labelling requirements for appliances containing hazardous substances
lead to attention in handling those devices especially if safety at work is affected.
But in case of valuables, this might produce opposite effects. (The message
“don’t waste this product – valuables included” will encourage people to keep
the useless product instead of dropping it into the correct recycling bin).
• Labels indicating correct disposal may also be helpful, but are very often ignored
if there is no obvious danger for the waste producer in case of acting against the
label’s advice. In the future, invisible identification tags like the RFID technique
could help to sort out the devices in question from the waste stream.
• For persistent hazardous substances, inventories covering production, trade,
application fields, and disposal are extremely helpful to identify sources and
sinks in the technosphere and in the environment. Data covering the flows of
valuable resources are necessary as well and should be documented by the
responsible parties dealing with these resources. Material balances based on
the inventories are helpful also to get an idea of unknown sources and undetected
leakages in the technosphere, even if the figures sometimes might be
questionable.
• The DPSIR scheme is a reasonable approach also in the case of valuable
resources, if we define the impact as (potential) shortage of a resource. This is
an input-oriented problem caused by high anthropogenic flows of a scarce non-
renewable resource.
More examples should be checked using this approach to learn from the man-
agement of hazardous substances for the management of resources.

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Toxicological Characterization of Waste-Related
Products Using Alternative Methods:
Three Case Studies

Diego Baderna, Nazanin Golbamaki, Silvia Maggioni, Monica Vaccari,
Annamaria Colacci, and Emilio Benfenati

Abstract The characterization of toxicological impact of chemicals and mixtures
from environmental matrices is a critical point in the assessment of adverse effects
induced in human and ecological targets. In fact, the toxicity of most of the
environmental mixtures is still under investigation due to the possibility of synergic
or antagonistic effects of the components. Moreover, in some cases, the toxicity of
identified chemicals is not already well known and it could be an additional matter
of concern.
Encouraged by recent legislations all over the world aimed to protect human
health and environment, alternative methods have proved their abilities to assess
the toxicity of chemicals. Hence, a possible solution to the characterization of the
toxicological and ecotoxicological risk of the chemicals could be represented by the
application of in silico and in vitro techniques.
However, only a limited number of studies using alternative methods (testing
and non-testing) are present in the scientific literature but the studies are increasing
and becoming more important and spread day by day, in particular for the evalua-
tion of mixtures derived from environmental matrices.
Among the possible solutions, in vitro assay and QSARs models are the most
applied approaches in the field of environmental research and risk assessment.
In this chapter three case studies are introduced as examples of the application of
alternative methods for the toxicological characterization of waste-related products.

D. Baderna (*), N. Golbamaki, S. Maggioni, and E. Benfenati
Laboratory of Environmental Chemistry and Toxicology Mario Negri Institute,
Via Giuseppe La Masa 19, 20156 Milan, Italy
e-mail: diego.baderna@marionegri.it
M. Vaccari and A. Colacci
Center for Environmental Carcinogenesis and Risk Assessment, Environmental Protection and
Health Prevention Agency – Emilia Romagna Region, Viale Filopanti 20, 40126 Bologna, Italy

B. Bilitewski et al. (eds.), Global Risk-Based Management of Chemical Additives II: 171
Risk-Based Assessment and Management Strategies, Hdb Env Chem (2013) 23: 171–206,
DOI 10.1007/698_2012_176, # Springer-Verlag Berlin Heidelberg 2012,
Published online: 24 July 2012
172 D. Baderna et al.

The first case is an integrated approach based on chemical analyses, risk
assessment, and in vitro assays for the investigation of the toxicity of a leachate
produced by a modern industrial landfill in Italy.
The second example focuses on qualitative evaluation of cancerogenic potential
of some perfluorinated compounds using both QSARs models and an in vitro cell
transformation assay.
Finally, a QSAR evaluation of different chemicals from waste-related products
and recycling is shown in order to underline how in silico models can be used as a
valid tool to fill in the gaps and to obtain information on toxicological profile and
physicochemical information on compounds. In particular, a focus on compounds
suggested by EU project “Riskcycle” is presented.

Keywords Alternative methods, Chemical carcinogenicity, Mixtures, Toxicologi-
cal profile

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
2 Alternative Methods for the Study of Landfill Leachate Toxicity . . . . . . . . . . . . . . . . . . . . . . . . 175
3 Qualitative Evaluation of Carcinogenic Potential of Some PFCs Using In Silico
and In Vitro Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
3.1 QSARs Approach and Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
3.2 BALB/c CTA Approach and Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
3.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
4 Comparative QSAR Evaluation of Toxicological Properties of Chemicals Suggested
by EU Riskcycle Project . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202

1 Introduction

The assessment of acute and chronic adverse effects induced by chemicals in both
human and ecological (plants, animals, ecological chains, and ecosystems) targets
is one of the most important scopes of environmental toxicology and sciences. In
particular, the evaluation of the risk derived from the exposure to complex mixtures
from environmental and diet sources is a challenging task which needs strategies,
efforts, and time to reach the objectives of health protection.
Moreover, nowadays there are still thousands of chemicals, including industrial
xenobiotics, natural products, and pesticidal active and inert ingredients, with the
potential for significant human exposures but for which toxicity information is
either limited or nonexistent [1]. The requirements arising from the regulation and
the need to better characterize the toxicological, ecotoxicological, and environmen-
tal properties of an increasing number of chemicals have the consequence of an
increased number of animal experiments to provide answer to these data needs.
Toxicological Characterization of Waste-Related Products Using Alternative. . . 173

The data gap could be solved conducting animal testing in rodents and other
species which requires high cost and time: thousands of animals are used to
perform a complete set of regulatory tests for a single chemical and costs millions
of dollars [2].
Carcinogenicity and chronic, reproductive, and developmental toxicity are the
most animal-consuming studies.
However, this request of more animal testing faces several issues. There is an
ethical concern on the millions of animals used every year for experiments. These
tests are also those more expensive, and thus this poses questions about the costs for
these experiments and the resources to cover them. Many of these tests, especially
the chronic ones, require long times, years in some cases. The number of available
laboratories in Europe to cover this potential request is insufficient. For all these
reasons, some European regulations foresee the use of methods alternative to
animal tests, such as the REACH legislation, and actually the cosmetics directive
foresees the complete ban of animal tests for cosmetics by 2013.
Alternative methods includes “any method that can be used to Replace, Reduce
or Refine the use of animal experiments in biomedical research, testing or educa-
tion” [3]. The term “alternative” includes all procedures which can completely
replace the need for animal experiments, reduce the number of animals required, or
diminish the amount of distress or pain suffered by animals in meeting the essential
needs of man and other animals [4].
Replacement consists in the use of non-sentient organisms (e.g., microorg-
anisms, metazoan parasites, and higher plants) as possible alternatives of higher
animals for experiments, also the including stages of development where it is
recognized that organism is able to feel pain. Experiments using these materials
could be defined “absolute replacement” when no higher animals were required at
any stage or “relative replacement” if methods require non-sentient material with
animal origins. The Reduction occurs when a method reduces the number of
animals needed to perform a specific assay, while still achieving the same level
of information (best quality information with the smallest possible number of
animals). Refinement is referred to all changes in protocols that reduce the inci-
dence or severity of distress experienced by laboratory animals.
An important point, made by the European Centre for the Validation of Alterna-
tive Methods (ECVAM), is that these 3 aspects (3Rs) should not be considered as
alternatives that could replace each other, but as parts of an integrated system which
should lead to progress in the development of non-animal tests and testing
strategies. Another important key point recently defined by ECVAM is that the
use of existing information must be maximized instead of testing methods.
For this purpose some useful data can be:
• The production volume
• The reasons for uses
• The studies of occupational or environmental exposure
• The physicochemical properties of chemicals (for example stability, solubility,
pH, octanol-water partition coefficient, protein binding)
174 D. Baderna et al.

Fig. 1 Classification of alternative methods

• Epidemiological investigations
• Post-marketing surveillance for medicines, cosmetics and household or agricul-
tural products
Alternative methods could be classified into testing (ATMs) and non-testing
methods (ANTMs) (Fig. 1) [5]. The first class includes experiments on lower
organisms (bacteria, fungi, plants, invertebrate animals), studies on vertebrates at
early stages of development (before they become sentient/protected animals) and
studies on in vitro systems of various kinds (including whole perfused organs, tissue
slices, cell, tissue and organotypic cultures, and subcellular fractions). The second
group is represented by predictions based on structure-activity relationships (SARs)
(qualitative and quantitative mathematical models, and the use of read-across data
from related chemicals) or the biokinetic modeling of physiological, pharmacolog-
ical, and toxicological processes.
Among the possible alternative methods, in vitro assay (for ATMs) and quanti-
tative structure-activity relationships (QSARs) models (for ANTMs) are the most
applied approaches in the toxicological and ecotoxicological evaluation of
chemicals’ profiles, even in the field of environmental research and risk assessment.
Encouraged by recent legislations all over the world aimed to protect human
health and environment, alternative methods have proved their abilities to assess
the toxicity of chemicals. Hence, a possible solution to the characterization of the
toxicological and ecotoxicological risk of the chemicals could be represented by the
application of in silico and in vitro techniques.
However, only a limited number of studies using alternative methods (testing
and non-testing) are present in the scientific literature but the studies are increasing
and becoming more important and spread day by day, in particular for the evalua-
tion of mixtures derived from environmental matrices.
In this chapter, three case studies are introduced as examples of the application
of alternative methods for the toxicological characterization of waste-related
products.
Toxicological Characterization of Waste-Related Products Using Alternative. . . 175

The first case is an integrated approach based on chemical analyses, risk
assessment, and in vitro assays to investigate the toxicity of a leachate produced
by a modern industrial landfill in Italy.
The second example focuses on qualitative evaluation of carcinogenic potential
of some perfluorinated compounds (PFCs) using both QSARs models and an
in vitro cell transformation assay (CTA).
Finally, a QSAR evaluation of different chemicals from waste-related products
and recycling is shown in order to underline how in silico models can be used as a
valid tool to fill in the gaps and to obtain information on toxicological profile and
physicochemical information on compounds. In particular, a focus on compounds
suggested by EU project “Riskcycle” is presented.

2 Alternative Methods for the Study of Landfill Leachate
Toxicity

Solid wastes constitute an important and emerging environmental problem at a
global scale. A recent study from Bakare et al. suggests that the production of solid
wastes varies from 0.5 to 4.5 kg per person per day in different regions of the world
[6]. It is therefore clear that proper management of the waste problem must be
nowadays at the center of the management policies of each nation in order to reduce
the local and the global impact.
The most common methods for dumping off wastes are the storage in landfills or
the incineration in incinerator plants.
Between these two solutions, landfills are considered the most widely practiced
methods for the disposal of municipal solid waste (MSW): actually up to 95% total
MSW collected worldwide is disposed off in landfills [7]. Landfilling is a funda-
mental step in any waste management strategy but it can constitute a hazard for the
environment in the long time. Generally, landfills will produce mainly two kinds of
by-products: a highly toxic leachate and a significant amount of landfill gases. Gas
components can be partly used to produce energy while liquid residues could not be
used for energetic purpose. Leachate and gas control measures are very important in
order to reduce the overall environmental impact from a waste disposal site [8]. The
need to protect the environment from potential landfill emissions makes risk
assessment a decision tool of extreme necessity [9].
Landfill leachate is generated by the infiltration and percolation of water (not
only mainly rainfall but also groundwater, runoff, or flood water) into and through
the waste layers of a landfill site. From a toxicological point of view, leachate is the
results of a combination of physical, chemical, and microbial processes in which
pollutants transfer from the waste material to the percolating water, creating a
water-based solution that may be harmful to organisms, including human and
environmental receptors. In fact, due to its intrinsic properties and composition,
small amounts of leachate could pollute large volume of groundwater, rendering
176 D. Baderna et al.

Fig. 2 Design of the experiment for the investigation of leachate toxicity (modified from [17])

them unusable for domestic and many other purposes. More than 200 organic
compounds have been identified by previous studies in municipal landfill leachates:
inorganic salts, heavy metals, and xenobiotic organic compounds [10–12].
Different international legislations and guidelines have been released to under-
line and highlight the role of ecotoxicological and toxicological risk assessment
(ERA and HRA) methodologies in the last 20–30 years [13–16]. These technical
methodologies could also be applied for the assessment and the evaluation of
pollutants from landfills, facing one of the major environmental issues in Europe
due to the large number of sites and to the importance of groundwater protection.
A recent study published by Baderna et al. in 2011 describes a combined method
to investigate the toxicity of an industrial landfill’s leachate which is based on a
triad approach including chemical analyses, risk assessment, and in vitro assays
[17]. Moreover, to verify the applicability and the robustness of the proposed
method, the approach was applied on a real case study: a controlled, ISO-14001
certified landfill for nonhazardous industrial waste and residual waste from the
treatment of MSW in northern Italy for which data on the presence of leachate
contaminants are available from the last 11 years.
First step of the approach is the chemical characterization of leachate using well-
established analytical techniques (Fig. 2): GC-MS for polar organic compounds
(POCs), HRGC-MS for PCDD/Fs, PCBs and PAHs [18], atomic absorption spec-
trometry for heavy metals and ion chromatography for ammonia.
Regarding POCs, eight compounds (see Table 1) were selected as “indicators”
from the qualitative analysis of leachate due to their frequent detection, to their
abundance, and to their absence in groundwater wells monitored upstream the
landfill. The selected compounds include plasticizers or their degradation products,
insect repellent and natural compounds resulting from anthropogenic pollution.
Levels of analyzed compounds were comparable with those reported in previous
studies with the exception of cadmium, ammonia, 2(3H)benzothiazolone, and
bisphenol A, which were higher than the published data regarding long-term
composition of MSW landfill leachate from some European MSW landfills while
Toxicological Characterization of Waste-Related Products Using Alternative. . . 177

Table 1 Selected polar Indicator POCs
organic compounds (POCs)
2-Phenyl-2propanol
for the quantitative analysis
2-Ethyl hexanoic acid
2,2,6,6-Tetramethyl-4-piperidinol
Nicotine
Bisphenol A
a,a,a,a-Tetramethyl-1,4-benzenedimethanol
N,N-Diethyl-m-toluamide
2(3H)-Benzothiazolone

Fig. 3 The hypothesis for the risk assessment (modified from [17])

no comparative data are reported in the literature for other compounds with
recognized carcinogenic potential such as dioxins, PCBs, and PAHs.
Data from chemical characterization were used to estimate possible adverse
effects on humans and the environmental receptors. Following previously
published works [11, 19], a hypothetic scenario was set up to assess the risk
posed by these non-conventional matrix: an accidental leachate release into ground-
water resulting in 1:100 and 1:1,000 dilutions of the leachate compounds, which
have been subjected to dilution as the leachate mixes with the groundwater (Fig. 3).
Human risk assessment (HRA) was done applying guidelines from the Italian
Institute for Environmental Protection and Research (ISPRA) and selecting water
ingestion as route of exposure for human health assessment [20]. According to the
178 D. Baderna et al.

guidelines, for each compound, chronic daily intake (CDI), Hazard Index (HI) for
toxic compound and Cancer Risk (CR) for carcinogenic effects were calculated and
exposures associated with HI<1 and CR<1E-6 were deemed negligible.
For the ecological assessment, risk analysis was based on the traditional PEC/
PNEC ratio (Hazard Quotient) where PEC is the predicted environmental concen-
tration (resulting from chemical analysis) and PNEC the predicted no-effect con-
centration. Ecological assessment for aquatic species was based on rainbow trout or
fathead minnow while terrestrial assessment was based on small rodents like mice
rats and rabbits. Exposures associated with HQ<1 were considered negligible.
Reference toxicological values for HRA for the selected pollutants were
obtained from ISS/ISPESL [21] and IRIS [22] databases or derived from animal
in vivo studies (rat or mouse) and using appropriate safety factors while PNEC
concentrations were obtained from previously selected peer-reviewed freely avail-
able databases [23] such as ECOTOX [24], ChemIDPlus advanced [25] and specific
reviews.
The first innovation introduced by the work is the approach used in the case of
missing data: human toxicological and ecotoxicological values were predicted
using freely available QSAR models like Toxicity Estimation Software Tool
(T.E.S.T.) v 3.2 [26] and ToxBoxes [27] (nowadays ToxBoxes is no longer free).
The evaluation of risk has underlined the possible adverse effects both on human
health after the exposure to drinking water contaminated by landfill leachate and on
small rodents and aquatic species at the hypothesized condition: for humans, the
estimated toxic effects of the raw leachate are mainly due to the levels of ammonia
and cadmium and carcinogenic effects are induced by arsenic first and then by
PCBs and PCDD/Fs while ecological potential risk is mainly attributable to the
concentration of inorganic compounds, in particular ammonia for small rodents,
cadmium, ammonia, and heavy metals for fishes.
The second innovative peculiarity is the application of HRA-oriented in vitro
investigation: a human in vitro model has been used to obtain more information on
the effect of leachate exposure and toxicity accounting of not only the toxicity of
hydrophilic and lipophilic compounds but also the effects of whole leachate as a
complex mixture.
Researchers focused on the metabolically competent human hepatoma cell line
HepG2 as a model of human liver. HepG2 cells are a well-known hepatoma cell line
that retains many of the morphological characteristics of liver parenchymal cells.
This model is often used as a useful tool for HRA/ERA-oriented chemical risk
assessment due to the expression of antioxidant and xenobiotic metabolizing
enzymes (in particular phase I and phase II enzymes responsible for the
bioactivation/detoxification of various xenobiotics) that can be induced or inhibited
by dietary and non-dietary agents [28–30].
Screening assays were used to study the effects on cell proliferation and cyto-
toxicity of whole leachate and relative organic and hydrophilic extracts on cell
model after 24–72 h of exposure.
According to the authors, no study has previously been setup to investigate the
potential hepatotoxicity of leachate using in vitro models. Results from the in vitro
study (Fig. 4) clearly indicate that the inhibition of cell proliferation by the raw
Toxicological Characterization of Waste-Related Products Using Alternative. . . 179

a 2.2

2

1.8
Abs @ 490 nm

1.6

1.4

1.2

1

0.8

0.6

0.4
0 24 48 72
Time (h)
CTR Leachate 2.5% v/v Leachate 10% v/v
Leachate 30% v/v
Leachate 1.2% v/v Leachate 5% v/v Leachate 20% v/v

b 2.2

2

1.8

1.6
Abs @ 490 nm

1.4

1.2

1

0.8

0.6

0.4

0.2
0 24 48 72
Time (h)
CTR AE 2.5% v/v AE 10% v/v
AE 30% v/v
AE 1.25% v/v AE 5% v/v AE 20% v/v

c 2.2

2

1.8

1.6
Abs @ 490 nm

1.4

1.2

1

0.8

0.6

0.4
0 24 48 72
Time (h)
CTR OE 2.5% v/v OE 10% v/v
OE 30% v/v
OE 1.25% v/v OE 5% v/v OE 20% v/v

Fig. 4 Leachate toxicity: effects of whole leachate (a), aqueous/hydrophilic phase (b) and
organic/lipophilic phase (c) on HepG2 cells (modified from [17])
180 D. Baderna et al.

leachate is induced by the hydrophilic components that remain, after organic
extraction, in the aqueous phase such as ammonia and heavy metals, while the
organic components do not show any effect.
Another peculiarity of the study is that the use of a biological system has allowed
the authors to hypothesize a possible mechanism of action of the leachate as a
mixture, hypothesis that could have been drafted on the basis of the only knowledge
derived by chemical analysis. Researchers suggest that leachate inhibits cell prolif-
eration at low doses probably inducing a reversible cell cycle arrest that becomes
irreversible at high doses, probably due to leachate-induced oxidative stress. This
activity is mainly due to the chemical compounds extracted in the aqueous phase.
Similar effects were noticed by previous investigations on other human cells
(human peripheral blood lymphocytes and a human breast cancer cell line, MCF-
7) [31, 32], supporting the hypothesis that cells that survive the initial insult from
leachate constituents maintains the potential to proliferate until the effects on cell
metabolism lead to death.
Summarizing, this first example of toxicological characterization of waste-
related products using alternative methods clearly suggests that:
– Chemical characterization alone is not sufficient to understand the overall
toxicity of conventional and unconventional environmental matrices;
– Risk assessment of landfill leachate, which is traditionally based on chemical
analyses of specific compounds, is not sufficiently developed to take into
account interactions among chemicals in the complex mixtures;
– Bioassays and in vitro human models can be used to characterize the toxicity of
leachate integrating the biological effects of all its constituents, in contrast to
chemical analyses;
– The evidences provides by ERA and HRA seems to be confirmed by in vitro
results;
– Each of the three above-mentioned components has advantages and disadvan-
tage which could be offset by the integration of different approaches.
The study on the landfill leachate, shown here as an example application of the
method, has demonstrated how information derived from individual approaches
provides a valuable support to one another.

3 Qualitative Evaluation of Carcinogenic Potential
of Some PFCs Using In Silico and In Vitro Methods

Carcinogenicity is one of the toxicological endpoints that pose the highest concern
for human health. Nowadays, protection against cancer resulting from exposure to
chemicals in the environment is a critical goal in public health management.
According to the definition provided by Pitot [33], “carcinogen” is an agent
whose administration to previously untreated animals leads to a statistically
Toxicological Characterization of Waste-Related Products Using Alternative. . . 181

significant increased incidence of neoplasms of one or more histogenetic types as
compared with the incidence in appropriate untreated animals.
The occurrence of cancer is complex and not yet completely clarified process: a
tumor is formed by millions of clones originating from one initial cell that has
accumulated genetic and epigenetic alterations leading to the transformation into a
cancer cell. The possible factors involved in neoplastic transformation of cells and
the subsequent development of cancer are manifold: in addition to endogenous
factors (e.g., genetic predisposition, immune system damage, and chronic inflam-
mation), there are indeed numerous exogenous or environmental factors which
serve as causative or tumor-promoting agents. Exposure to chemicals, dietary
habits, lifestyle, viruses, and radiation are important examples of exogenous
factors.
After the exposure to carcinogens, the occurrence of cancer is the final stage of
sequential processes. Studies using animal models, in vitro models and epidemio-
logical studies have shown that the pathogenesis of cancer is a multistep process
which can be divided, at least, into three distinct phases: initiation, promotion, and
progression. Initiation is the first stage of carcinogenesis and it is caused by
irreversible genetic mutations that make a normal cell more susceptible to malig-
nant evolution and immortality. In the promotion stage, the initiated cell interacts
with a tumor promoting agent that does not directly interact with the cellular DNA
but it is nevertheless able to induce different cascades of biological effects resulting
in cellular new properties.
The progression is the third and final stage of carcinogenesis: cells derived from
the original initiated cell, whose growth was accelerated in the promotion step,
acquire full malignant phenotype, by accumulating more genetic damages, most of
them affecting genes of cell cycle and growth control. The progression phase is
irreversible. Malignant cells appear morphologically different: they are genetically
unstable, grow faster, and acquire the ability to invade surrounding tissues and to
metastasize.
Several chemicals can act as initiators and/or promoting agents participating
actively in the process of carcinogenesis and also producing synergistic effects
when taken simultaneously via multiple routes of exposure.
Exposure assessment of general population and workers to carcinogens is
therefore a critical prerequisite for risk assessment to ensure an adequate level of
health protection. Since cancer represents the world’s leading cause of death as well
as the highest economic toll among diseases, due to premature death, disabilities,
treatments, not only would cancer prevention mean to increase life expectancy and
quality, by reducing loss and suffering, but also to lower its huge economic impact.
In recent decades, the development of chemical, biochemical, and biological
techniques has allowed the creation of analytical tools which can be used to
facilitate the identification of the mechanisms involved in neoplastic trans-
formation. Animal models remain, however, the most widely used approach of
investigation. Cancer bioassays are usually conducted in rodents (rats and
mice) and the experimental protocol takes 18–24 months and it is followed by
extensive histopathological and statistical analysis. The procedure is time and
182 D. Baderna et al.

money-consuming and the extrapolation of results from animal model to humans is
often difficult. Although many human carcinogens have been predicted on the basis
of results from animal models, it is often pointed out the representativeness of the
animal model for human carcinogenicity. Species-specific susceptibility, different
metabolism, and especially the treatment schedule at very high doses of chemicals
are the most debated points. Animal are often treated at doses that are not represen-
tative of real human exposure. High doses may lead to impairment of the natural
mechanisms of defense of the organism, such as DNA repair and metabolic
detoxification, that may be overwhelmed by high chemical concentrations. More-
over, while the effects induced by genotoxic compounds are commonly considered
to be linear with the applied dose, even at low exposures, non-genotoxic
compounds behavior is quite unpredictable.
In recent years, the scientific community has focused on the need to develop
alternative methods to animal experiments, including cell-based in vitro methods
and in silico models, based on statistics and informatics.
In vitro models could be used to study the molecular mechanisms involved in the
process of neoplastic transformation and as screening tools for the classification of
the carcinogenic potential of a substance. Among the in vitro tests available to the
scientific community, the CTA may represent an important tool for the identifica-
tion of carcinogens, particularly those that are not identifiable by classic mutage-
nicity tests such as the Ames test.
Compared to animal assays, CTA is faster and cheaper. In vitro CTAs have been
shown to involve a multistage process that closely resembles some stages of in vivo
carcinogenesis and have the potential to detect both genotoxic and non-genotoxic
carcinogens.
One of the most used transformation protocol is represented by the BALB/c 3T3
model, which shows a high correlation with the in vivo carcinogenesis and is able to
discriminate between substances that act at different stages of carcinogenesis
process, as initiating or promoting agents. BALB/c 3T3 cells are immortalized
mouse embryonic fibroblasts that are adapted to grow in vitro culture, where they
can divide indefinitely, while retaining some characteristic properties of normal
cells, like the inhibition of cell division occurring when cells reach the confluence
(contact inhibition). The treatment with a potential carcinogenic agent induces the
loss of contact inhibition.
Cells do not stop their proliferation upon reaching confluence, pile up in “stacks
(foci)” of morphologically transformed cells that can be considered as an endpoint
of neoplastic transformation (Fig. 5).
The possible use of the BALB/c 3T3 CTA is mentioned in various recent testing
strategies including the supplemental data for pharmaceuticals and the guidance on
information requirements and chemical safety assessment for REACH [34, 35].
In this chapter we will introduce and discuss the use of alternative methods to
evaluate the carcinogenic potential of some PFCs. In detail, in silico (QSAR)
models and BALB/c 3T3 CTA will be used to investigate the issue.
PFCs are a large group of chemicals characterized by a fully fluorinated hydro-
phobic chain and an hydrophilic head. These compounds are often used as coating
Toxicological Characterization of Waste-Related Products Using Alternative. . . 183

Fig. 5 BALB/c 3T3 cell transformation assay: example of focus induced in BALB/c 3T3 clone
A31-1-1 after exposure to a carcinogenic compound. Cells are stained with Giemsa stain

agents (textile products, packaging products, cookware, and food contact papers)
due to their ability to repel both water and oils. Nowadays they are internationally
recognized as global contaminants [36–38].
Several studies have suggested that some critical adverse effects like peroxisome
proliferation, hepatotoxicity, immunotoxicity, and developmental toxicity may be
associated with chemical exposure to PFCs, particularly to PFOS (perfluorooctane
sulfonate) and PFOA (perfluorooctanoic acid), two ubiquitous persistent organic
pollutants with possible environmental and human health risks.
Only a very limited number of strong evidence is present in the scientific
literature and guidelines about the correlation between PFCs and cancer [39–41].

3.1 QSARs Approach and Results

For the in silico evaluation of carcinogenic potential of PFCs, 16 compounds were
selected (see Table 2).
For each selected PFC, a profile was edited including the name of the compound,
its CAS (Chemical Abstracts Service) number and the SMILES (Simplified Molec-
ular Input Line Entry System) formula.
Using SMILES as input, carcinogenic potential was evaluated using four differ-
ent internationally recognized QSARs models: VEGA, ToxTree, Lazy structure-
activity relationships (Lazar), and Deductive Estimation of Risk from Existing
Knowledge (DEREK) for Windows. VEGA, ToxTree, and Lazar are freely avail-
able models while DEREK requires an annual fee.
184

Table 2 Selected perfluorinated compounds (PFCs) for the QSARs analysis
ID Acronym Name CAS SMILES
1 PFOS Perfluorooctane sulfonic acid 1763-23-1 C(C(C(C(C(C(C(C(S(¼O)(¼O)O)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)(F)F
2 PFOA Perfluorooctanoic acid 335-67-1 C(C(C(C(C(O)¼O)(F)F)(F)F)(F)F)(C(C(C(F)(F)F)(F)F)(F)F)(F)F
3 PFNA Perfluoro-n-nonanoic acid 375-95-1 O¼C(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F
4 PFBS Perfluorobutanesulfonic acid 375-73-5 OS(¼O)(¼O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F
5 POSF Perfluorooctanesulfonyl fluoride 307-35-7 C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(C(C(C(S(¼O)(¼O)F)(F)F)(F)F)(F)F)(F)F
6 PFOSA Perfluorooctanesulfonamide 754-91-6 S(¼O)(¼O)(C(C(C(C(C((F)(F)C(F)(F)C(F)(F)C(F)(F)F)(F)F)(F)F)(F)F)(F)F)N
7 PFDA Perfluorodecanoic acid 335-76-2 C(C(C(C(C(C(O)¼O)(F)F)(F)F)(F)F)(F)F)(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F
8 PFHxA Perfluorohexanoic acid 307-24-4 O¼C(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F
9 PFBA Perfluorobutanoic acid 375-22-4 C(C(C(O)¼O)(F)F)(C(F)(F)F)(F)F
10 PFUnDA Perfluoroundecanoic acid 2058-94-8 C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(C(C(C(C(¼O)O)(F)F)(F)F)(F)
F)(F)F
11 PFDoDA Perfluorododecanoic acid 307-55-1 O¼C(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)
(F)C(F)(F)F
12 PFHxS Perfluorohexane sulfonate 355-46-4 O¼S(¼O)(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F
13 PFHpA Perfluoroheptanoic acid 375-85-9 O¼C(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F
14 PFTA Perfluorotetradecanoic acid 376-06-7 O¼C(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)
(F)C(F)(F)C(F)(F)C(F)(F)F
15 PFPeA Perfluoro-n-pentanoic acid 2706-90-3 O¼C(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F
16 PFOSAA N-Ethyl-N-((heptadecafluorooctyl) 2991-51-7 C(C(C(C(S([N@@](CC(¼O)[O-])CC)(¼O)¼O)(F)F)(F)F)(F)F)(C(C(C(C(F)(F)F)
sulfonyl)glycine potassium salt (F)F)(F)F)(F)F)(F)F.[K+]
D. Baderna et al.
Toxicological Characterization of Waste-Related Products Using Alternative. . . 185

VEGA platform (http://www.vega-qsar.eu/) provides a series of QSAR models
for regulatory purposes, including mutagenicity, carcinogenicity, developmental
toxicity, skin sensitization, Fathead Minnow LC50 at 96 h, Bioconcentration factors
(BCF), persistence, and LogP.
The VEGA Carcinogenicity Classification Model provides a qualitative predic-
tion of carcinogenic potency according to specific requirements of chemical regu-
lation and extends the original freely available CAESAR model (http://www.
caesarproject.eu/software): based on Counter Propagation Artificial Neural Net-
work algorithm, the output of the neural network is if predicted compound could be
carcinogenic or non-carcinogenic compounds based on artificial neural network
algorithm [42]. Moreover, VEGA checks some Structural Alerts (SAs) in the
compound structure providing a remark about the presence of some fragment
related to a possible carcinogenic activity, if some SAs matches are found.
As a result, VEGA creates a PDF file that contains all the information about the
prediction, including the final assessment of the prediction, the list of the six most
similar compounds found in the training and test set of the model, the list of all
Applicability Domain indices and a reasoning on SAs with a brief explanation of
their meaning.
Lazar (http://lazar.in silico.de/predict) is a k-nearest-neighbor approach to pre-
dict chemical endpoints from a training set based on structural fragments [43]. It
derives predictions for query structures from a database with experimentally deter-
mined toxicity data [43]. Model provides prediction for four endpoints: Acute
toxicity to fish (lethality): Fathead Minnow Acute Toxicity (LC50), Carcinogenic-
ity, Mutagenicity, and Repeated dose toxicity.
Focusing on carcinogenicity model, predictions could be done using six different
models based on DSSTox datasets to make a qualitative evaluation of carcinoge-
nicity on hamster, mouse, rat, and cells.
Toxtree (http://toxtree.sourceforge.net/) is a full-featured and flexible open
source application which can be used to estimate various kinds of toxic hazard by
applying a decision tree approach.
The platform includes different decision trees for the following endpoints: the
estimation of Threshold of Toxicological Concern (TTC), aquatic modes of action
[44], skin and eye irritation and corrosion, mutagenicity and carcinogenicity [45],
in vivo micronucleus assay, identification of Michael Acceptors and biodegradation
potential [46].
Regarding the carcinogenicity model, Toxtree includes a decision tree for
estimating carcinogenicity and mutagenicity based on the “Benigni/Bossa
rulebases” which estimate potential carcinogenicity and mutagenicity using SAs
and different QSAR models.
In the latest version of Toxtree, another rulebase has been implemented for the
in vivo micronucleus assay (ToxMic rulebase) which identifies 30 SAs from the
Benigni-Bossa rulebase for genotixic carcinogenicity and five alerts specific for
the micronucleus assay [47]. The occurrence of micronucleus in cells, tissue, or
blood is linked to irreversible mutations which can also lead to cancer.
186 D. Baderna et al.

DEREK [48] is an expert knowledge base system which predicts carcinogenicity
merging a series of rules based on laboratory studies on different species [49].
DEREK studies substructures known to have adverse toxicological properties SAs,
looking for matches to substructures in the target molecule. The presence of an alert
is related to the carcinogenicity of the compound processed. Potentially toxic
substructures (toxicophore) are identified by matching patterns of atoms and
bonds in the rule base to the target molecule. Each possible toxicophore is then
further evaluated by “reading” from the rule base a list of scope and limitations
questions.
Results of the QSAR analysis are shown in Tables 3, 4 and 5.
Results from VEGA underline the presence of 13 compounds with carcinogenic
activity and only two non-carcinogenic compounds (perfluorobutanesulfonic acid
and perfluorotetradecanoic acid). It is crucial to underline that for each selected
PFCs, VEGA provides a remarks about the “performance” of the prediction: in fact,
the model indicates that all the analyzed compounds are out of the VEGA applica-
bility domain.
Analyses from Toxtree indicate that no alerts for carcinogenicity were identified
in the selected PFCs applying the Benigni-Bossa rulebases for carcinogenicity
while some positives matches has been registered regarding the presence of SAs
for in vivo induction of micronuclei for each PCFs, except for POSF (perfluorooc-
tanesulfonyl fluoride).
Regarding Lazar, different modules were applied. No evidence of carcinogenic
potential was recorded using the modules for multi cells (1), rat (2), single cell (3),
and hamster (6), while different results were obtained using ISSCAN (4) and mouse
(5) modules. Results from ISSCAN underline the presence of carcinogenic poten-
tial in ten PFCs while the module on mouse is not able to perform a prediction on
five compounds due to the absence of enough similar compounds in the dataset but
no evidence of carcinogenic potential was recorded for the other 11 compounds,
according to the above-mentioned modules.
Finally, results from DEREK clearly suggest that all the selected PFCs are non-
carcinogenic compounds. It is important to underline that in our application of
DEREK a compound was considered “non-carcinogenic” if the response was
“Nothing to report,” although this is not the intended use of the “Nothing to report”
output of the Derek for Windows software [50].

3.2 BALB/c CTA Approach and Results

The analyses using the LAZAR module 4 and VEGA have indicated that perfluor-
ooctanoic acid (PFOA) and perfluoro-n-nonanoic acid (PFNA) could be compounds
with carcinogenic potential.
So, to verify this hypothesis a CTA was set up using BALB/c 3T3 clone A31-1-1
cells.
Table 3 QSARs analysis of PFCs using VEGA and ToxTree
VEGA TOXTREE
Benigni Bossa rulebase SAs for in vivo micronucleus
for carcinogenicity assay in rodents
Compounds Response Note Response Response
PFOS Positive Compound is out of model Applicability No alerts for carcinogenic activity Positive SAs for the micronucleus
Domain assay
PFOA Positive Compound is out of model Applicability No alerts for carcinogenic activity Positive SAs for the micronucleus
Domain assay
PFNA Positive Compound is out of model Applicability No alerts for carcinogenic activity Positive SAs for the micronucleus
Domain assay
PFBS Non positive Compound is out of model Applicability No alerts for carcinogenic activity Positive SAs for the micronucleus
Domain assay
POSF Positive Compound is out of model Applicability No alerts for carcinogenic activity No alerts for the micronucleus
Domain assay
PFOSA Positive Compound is out of model Applicability No alerts for carcinogenic activity Positive SAs for the micronucleus
Domain assay
PFDA Positive Compound is out of model Applicability No alerts for carcinogenic activity Positive SAs for the micronucleus
Domain assay
PFHxA Positive Compound is out of model Applicability No alerts for carcinogenic activity Positive SAs for the micronucleus
Domain assay
PFBA Positive Compound is out of model Applicability No alerts for carcinogenic activity Positive SAs for the micronucleus
Domain assay
PFUnDA Positive Compound is out of model Applicability No alerts for carcinogenic activity Positive SAs for the micronucleus
Domain assay
Toxicological Characterization of Waste-Related Products Using Alternative. . .

PFDoDA Positive Compound is out of model Applicability No alerts for carcinogenic activity Positive SAs for the micronucleus
Domain assay
PFHxS Positive Compound is out of model Applicability No alerts for carcinogenic activity Positive SAs for the micronucleus
Domain assay
PFHpA Positive No alerts for carcinogenic activity Positive SAs for the micronucleus
assay
187

(continued)
Table 3 (continued)
188

VEGA TOXTREE
Benigni Bossa rulebase SAs for in vivo micronucleus
for carcinogenicity assay in rodents
Compounds Response Note Response Response
PFTA Non Positive Compound is out of model Applicability No alerts for carcinogenic activity Positive SAs for the micronucleus
Domain assay
PFPeA Positive Compound is out of model Applicability No alerts for carcinogenic activity Positive SAs for the micronucleus
Domain assay
PFOSAA – Molecule has disconnected structure No alerts for carcinogenic activity Positive SAs for the micronucleus
assay
Note: VEGA version 2.1.3; ToxTree Version 2.5.0 - August 2011
D. Baderna et al.
Table 4 QSARs analysis of PFCs using Lazar
LAZAR
1 2 3 4 5 6
Compounds Response Response Response Response Response Response
PFOS Non-carcinogen Non-carcinogen Non-carcinogen Non-carcinogen Not enough similar compounds in Non-carcinogen
training dataset
PFOA Non-carcinogen Non-carcinogen Non-carcinogen Carcinogen Non-carcinogen Non-carcinogen
PFNA Non-carcinogen Non-carcinogen Non-carcinogen Non-carcinogen Non-carcinogen Non-carcinogen
PFBS Non-carcinogen Non-carcinogen Non-carcinogen Non-carcinogen Not enough similar compounds in Non-carcinogen
training dataset
POSF Non-carcinogen Non-carcinogen Non-carcinogen Non-carcinogen Not enough similar compounds in Non-carcinogen
training dataset
PFOSA Non-carcinogen Non-carcinogen Non-carcinogen Non-carcinogen Not enough similar compounds in Non-carcinogen
training dataset
PFDA Non-carcinogen Non-carcinogen Non-carcinogen Carcinogen Non-carcinogen Non-carcinogen
PFHxA Non-carcinogen Non-carcinogen Non-carcinogen Carcinogen Non-carcinogen Non-carcinogen
PFBA Non-carcinogen Non-carcinogen Non-carcinogen Carcinogen Non-carcinogen Non-carcinogen
PFUnDA Non-carcinogen Non-carcinogen Non-carcinogen Carcinogen Non-carcinogen Non-carcinogen
PFDoDA Non-carcinogen Non-carcinogen Non-carcinogen Carcinogen Non-carcinogen Non-carcinogen
PFHxS Non-carcinogen Non-carcinogen Non-carcinogen Non-carcinogen Not enough similar compounds in Non-carcinogen
training dataset
PFHpA Non-carcinogen Non-carcinogen Non-carcinogen Carcinogen Non-carcinogen Non-carcinogen
PFTA Non-carcinogen Non-carcinogen Non-carcinogen Carcinogen Non-carcinogen Non-carcinogen
PFPeA Non-carcinogen Non-carcinogen Non-carcinogen Carcinogen Non-carcinogen Non-carcinogen
Toxicological Characterization of Waste-Related Products Using Alternative. . .

PFOSAA Non-carcinogen Non-carcinogen Non-carcinogen Non-carcinogen Non-carcinogen Non-carcinogen
Note: 1 - DSSTox carcinogenic potency DBS MultiCellCall; 2 - DSSTox carcinogenic potency DBS Rat; 3 - DSSTox carcinogenic potency DBS SingleCell;
4 - DSSTox ISSCAN; 5 - DSSTox carcinogenic potency DBS Mouse; 6 - DSSTox carcinogenic potency DBS Hamster
189
190 D. Baderna et al.

Table 5 QSARs analysis of DEREK
PFCs using DEREK
Compounds Response
PFOS Non-carcinogenic
PFOA Non-carcinogenic
PFNA Non-carcinogenic
PFBS Non-carcinogenic
POSF Non-carcinogenic
PFOSA Non-carcinogenic
PFDA Non-carcinogenic
PFHxA Non-carcinogenic
PFBA Non-carcinogenic
PFUnDA Non-carcinogenic
PFDoDA Non-carcinogenic
PFHxS Non-carcinogenic
PFHpA Non-carcinogenic
PFTA Non-carcinogenic
PFPeA Non-carcinogenic
PFOSAA Non-carcinogenic

CTAs are possible in vitro alternatives to the standard approach for the assess-
ment of carcinogenicity (the 2-year bioassay in rodents), which have been shown to
be a multistage process able to model the most important stages of in vivo carcino-
genesis [50]. CTAs are faster and more economic than in vivo assay and they could
be a valid and useful screening tool for chemicals.
Actually, the BALB/c 3T3 test is mainly used:
– To screen chemicals for their potential carcinogenicity
– To provide useful ancillary information when the biological significance of the
bioassay result is uncertain
– To clarify in vitro genotoxic positive results by weight of evidence
– To screen for non-genotoxic carcinogens
– To demonstrate differences and similarities across a chemical class
– To screen for efficacy of chemopreventive agents
– To investigate tumor promotion activity
– For mechanistic studies of carcinogenicity
The endpoint of the BALB/c CTA is the carcinogenic conversion from non-
tumorigenic immortality to tumorigenicity resulting in focus formation and
anchorage-independent growth [51].
Focusing on PFOA and PFNA, the evaluation assay was set up in two phases:
– Cytotoxicity assay to evaluate the PFCs’ toxicity and to select the concentrations
for the transformation assay
– Transformation assay
As the first step, the toxicity of PFOA and PFNA was assessed using the colony
formation assay (Fig. 6): cells at the density of 250 cells/plate were seeded in
Toxicological Characterization of Waste-Related Products Using Alternative. . . 191

Fig. 6 BALB/c 3T3 cell transformation assay: Colony formation assay

60 x 15 mm Petri dishes and, after two days, were treated with different doses of
PFCs dissolved in DMSO. Five replicates for each concentration were done. After
2 days treatment medium was removed and cells were replenished with fresh
medium. Cells were maintained in culture for ten days, then fixed with methanol,
stained with 10% aqueous Giemsa and scored for colony formation. Only colonies
containing more than 50 cells were counted. Untreated BALB/c 3T3 cells and
vehicle-treated cells were used as negative controls. Results were expressed as
relative clonal efficiency (RCE) which estimates the per cent reduction of cell
clonal efficiency in treated groups as compared to that of the relative control
(vehicle-treated cells). Results of cytotoxicty assay are reported in Fig. 7. A dose
response relationship was obtained for both compounds. However, since PFNA is
more toxic than PFOA, no colonies were recorded after 250 mM PFNA treatment,
while a similar evidence was achieved only at the highest assayed dose of PFOA
(1,000 mM).
Based on these results, compounds were tested at five doses for CTA (Fig. 8).
Cells were seeded at a density of 3  104 cells/60 mm dish, incubated for 48 h and
then exposed to the tested compound at concentrations previously determined by
the cytotoxicity test. Ten replicates were carried out for each treatment.
Untreated BALB/c 3T3 cells and solvent-treated cells were used as negative
controls. Positive controls were represented by cells treated with the well-known
carcinogen 3-MCA (2.5 mg/mL). After 48 h, cells were replenished with fresh
normal culture medium and maintained in culture for 4–6 weeks, with biweekly
medium changes. Cells were then fixed with methanol, stained with 10% aqueous
Giemsa, and scored for foci formation. In order to calculate the number of cells
192 D. Baderna et al.

Fig. 7 BALB/c 3T3 cytotoxicity assay: red bar (NT) is untreated cells while green bar (DMSO) is
the vehicle control

Fig. 8 BALB/c 3T3 cell transformation assay: transformation assay protocol
Toxicological Characterization of Waste-Related Products Using Alternative. . . 193

12
11
10
9
8
0.4
TF (1E-4)

0.3

0.2

0.1

0.0
SO T

SO %
5%

O A
PF 100

O 0
PF 300

O 0

PF 00

N 0
00

5

0

0
PF 20

PF 40

5

12

20

25
N

PF C
1

5

1
M

A
0,

0,

A

A

A

A

A

A

A

A

A
N
O

O

N

N

N
PF

PF

PF

PF
M

M
D

D

Samples (µM)

Fig. 9 BALB/c 3T3 cell transformation assay: transformation frequency of PFOA and PFNA.
Red bar is the control group (untreated cells)

surviving the chemical treatment, colony-forming efficiency assays were also
performed in parallel with the transformation test.
The scoring of foci was carried out according to the recommended guidelines.
Only foci considered as positive (type III), showing deeply basophilic, dense
multilayering of cells, random cell orientation at all parts of the focus edge,
invasion into the surrounding contact-inhibited monolayer, and domination of
spindle-shaped cells, were counted.
Data was reported as transformation frequency (TF), calculated on the cells that
survived after chemical exposure. TF is expressed as a function of the total number
of foci per treatment divided by the number of surviving cells estimated from the
clonal efficiency observed in the cytotoxicity assay performed in parallel with the
transformation test [52].
Results are reported in Fig. 9: no significant increase of TF was recorded after
exposure to PFOA (100–500 mM) and PFNA (50–250 mM) suggesting that both
compounds do not have carcinogenic potential.

3.3 Conclusions

The potential for a compound to induce carcinogenicity is a crucial consideration
when establishing hazard and risk assessment of chemicals and pharmaceuticals in
humans [53]. To date, the standard approach to assess carcinogenicity at a regu-
latory level is the 2-year bioassay in rodents. According to the recent REACH
194 D. Baderna et al.

legislations, the use of alternative methods for carcinogenicity is strongly
recommended for the screening of chemicals.
Among possible alternative, QSARs models and the BALB/c 3T3 in vitro CTA
represent a possible solution. An example of the application of these methodologies
is reported in this chapter focusing on the evaluation of PFCs.
Most results from QSARs models underline that selected PFCs do not have a
carcinogenic profile. Only a model, VEGA, not only suggests the presence of
compounds with carcinogenic activity but also clearly indicates that all the
analyzed compounds are out of the VEGA applicability domain.
To verify the prediction from in silico approach, a BALB/c 3T3 CTA was
performed on PFOA and PFNA. Results from in vitro assay confirm the response
from QSARs models.
Results from this preliminary study suggest that a combined approach based on
alternative methods could be positively applied to chemical screening in order to
reduce the number of animal testing for carcinogenicity studies.
It is important to underline that the use of different models is strongly
recommended in case of QSARs evaluation in order to face the limitation of their
applicability domain and to produce a reliable judgment.

4 Comparative QSAR Evaluation of Toxicological Properties
of Chemicals Suggested by EU Riskcycle Project

One of the aims of EU project Riskcycle is to assemble and evaluate existing
information on the chemicals and especially the additives used in consumer and
industrial products with a special focus on the fate and behavior of these additives in
six product sectors: textile, electronics, plastics, leather, paper, and lubricants [54].
Selecting from scientific literature and reviews, Riskcycle researchers have
defined a preliminary list of 16 additives of interest which will be analyzed and
evaluated for a waste-related risk assessment: chosen compounds include
perfluorinated and brominated compounds, phthalates, phenols, and some heavy
metals (Table 6).
Within the project we also evaluated alternative methods as tools to obtain
information on the toxicological and physicochemical profile of the pollutants. In
this paragraph, an example of the application of QSARs models is reported: a
comparison is done between predicted values from different models or between
QSARs evaluation and experimental values from internationally recognized
databases.
From the preliminary list of 16 compounds of concern, 14 compounds have been
selected for the application of in silico methods because metals, and generally
inorganic compounds, cannot be subjected to QSARs analysis.
Different toxicological endpoints which can be useful for a risk-oriented
profiling have been evaluated:
Table 6 RISKCYCLE selected compounds
ID Name Acronym SMILES CAS Sector
1 Perfluoro octane sulfonate PFOS OS(¼O)(¼O) C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F) 2795-39-3 Lubricants
(F)C(F)(F)C(F)(F)C(F)(F)F
2 Perfluoro octanic acid PFOA OC(¼O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F) 335-67-1
(F)C(F)(F)F
3 (4-Nonylphenoxy)acetic NPAA CCCCCCCCCC1¼CC¼C(CCC(O)¼O)C¼C1 3115-49-9
acid
4 Hexabromo cyclododecane HBCDD C1C(CC(CC(CC(CC(CC1Br)Br)Br)Br)Br)Br 256937-99-4 Textiles
5 5-Chloro-2-(2,4-dichloro- Triclosan OC1¼CC(CI)¼CC¼C1OC1¼C(CI)C¼C(CI)C¼C1 3380-34-5
phenoxy)-phenol
(biocide)
6 Di-(2-ethylhexyl)-phthalate DEHP c1(c(C(OC[C@@H](CCCC)CC)¼O)cccc1)C(CC 117-81-7 Plastics
[C@@H](CCCC)CC)¼O
7 Lead – [Pb] 7439-92-1
8 2,2’,4,4’,5-Pentabromo- BDE 99 c1(cc(c(cc1Br)Br)Oc1ccc(cc1Br)Br)Br 60348-60-9 Electronics
diphenyl ether
9 2,2’,4,4’,6-Pentabromo- BDE 100 BrC1¼CC¼C(OC2¼C(Br)C¼C(Br)C¼C2Br)C 189084-64-8
diphenyl ether (Br)¼C
10 Decabromodiphenylether – BrC1¼C(Br)C(Br)¼C(OC2¼C(Br)C(Br)¼C(Br)C 1163-19-5
(Br)¼C2Br)C(Br)¼C1Br
11 Triphenylphosphate TPP O¼P(OC1¼CC¼CC¼C1)(OC1¼CC¼CC¼C1) 115-86-6
OC1¼CC¼CC¼C1
12 Mercury – [Hg]
Toxicological Characterization of Waste-Related Products Using Alternative. . .

13 Nonylphenol NPE CCCCCCCCCC1¼CC¼C(C¼C1)O 25154-52-3 Leather, paper
14 Bisphenol A BPA CC(C)(C1¼CC¼C(O)C¼C1)C1¼CC¼C(O)C¼C1 80-05-7
15 Isothiazolinones (biocides) – CN1SC(CI)CC1¼O 26172-55-4
16 – CN1SC¼CC1¼O 2682-20-4
195
196 D. Baderna et al.

– Genotoxicity/Mutagenicity (Ames Mutagenicity)
– Carcinogenicity
– Developmental toxicology
– Skin sensitization
– Bioconcentration factors (BCF)
– Aquatic toxicity: Daphnia magna 48 h LC50 and fathead minnow (fish) 96 h
LC50
– Acute toxicity: rat oral LD50
For a comparison, to obtain multiple values of each parameters six different
models have been applied: CAESAR, Toxtree, T.E.S.T., Lazar, and ECOSAR,
which are freely available, and ToxSuite (ACD/Labs) [55].
QSAR models addressing five endpoints relevant for REACH legislation have
been developed by the European funded CAESAR research project [56]. These
models are focused on BCF in fish, mutagenesis, carcinogenesis, developmental
toxicity, and skin sensitization. The developed models have been implemented into
a Java-based applet available through the Internet.
A similarity check is also implemented to compare the queried substances with
those used to develop the model and to verify how accurate their predicted values
were.
Toxtree [57] can be used to estimate various kinds of toxic hazard by applying a
decision tree approach.
The platform includes different decision trees for the following endpoints: the
estimation of TTC, aquatic modes of action, skin and eye irritation and corrosion,
mutagenicity and carcinogenicity, in vivo micronucleus assay, identification of
Michael Acceptors and biodegradation potential.
Regarding the carcinogenicity model, Toxtree includes a decision tree for
estimating carcinogenicity and mutagenicity based on the “Benigni/Bossa
rulebases” which estimate potential carcinogenicity and mutagenicity using SAs
and different QSAR models.
The US EPA T.E.S.T. is a downloadable program to estimate different toxico-
logical endpoints and physicochemical properties from molecular structure using a
variety of QSAR methodologies [58].
T.E.S.T allows you to estimate the value for 96 h fathead minnow LC50, 48 h
Daphnia magna LC50, 48 h Tetrahymena pyriformis IGC50, Oral rat LD50,
Bioaccumulation factor, Developmental toxicity, Ames mutagenicity, Normal boil-
ing point, Density, Flash point, Thermal conductivity, Viscosity, Surface tension,
and Water solubility.
Lazar [59] derives predictions for four endpoints: Fathead Minnow Acute
Toxicity (LC50), Carcinogenicity, Mutagenicity, and Repeated dose toxicity.
Focusing on carcinogenicity model, predictions could be done using six different
models based on DSSTox datasets to make a qualitative evaluation of carcinoge-
nicity on hamster, mouse, rat, and cells.
The US EPA Ecological Structure Activity Relationships (ECOSAR™) Class
Program estimates the aquatic toxicity of industrial chemicals, in particular
Toxicological Characterization of Waste-Related Products Using Alternative. . . 197

focusing on acute (short-term) toxicity and chronic (long-term or delayed) toxicity
for fish, aquatic invertebrates, and green algae using SARs [60]. Model is included
in the Estimation Program Interface (EPI) Suite, a Windows®-based suite of
physical/chemical property and environmental fate estimation programs developed
by the EPA’s Office of Pollution Prevention Toxics and Syracuse Research Corpo-
ration (SRC) [61].
ACD/Tox Suite is a collection of software modules that predict probabilities for
basic toxicity endpoints. Predictions are made from chemical structure and based
upon large validated databases and QSAR models, in combination with expert
knowledge of organic chemistry and toxicology. ToxSuite modules for Acute
Toxicity, Genotoxicity, Skin Irritation, and Aquatic Toxicity have been used.
The Acute Toxicity LD50 module provide predictions of LD50 (mg/kg) values
for rats and mice according to various routes of administration including oral
ingestion [62]. Moreover, experimental values (if present) and similarity to test
compound are shown for the five most similar structures from the training set.
The Ames test module of Genotoxicity predictor provides qualitative evaluation
of the mutagenic potential of compounds calculating by the probability of a positive
Ames test results [63]. Moreover, it is possible to visualize the genotoxic potential
of atoms or fragments of the compound’s structure by a dual-color mapping (red is
involved in genotoxicity, green is not involved).
The Irritation module estimates the potential of selected compound to cause eye
or skin irritation in standard rabbit Draize test [64].
Finally, the Aquatic Toxicity module predicts fish and daphnia toxicity
providing LC50 values (mg/L) for Pimephales promeals (Fathead minnow) and
Daphnia magna (Water flea). Experimental values (if present) and similarity to test
compound are shown for the five most similar structures from the training set [65].
Results from the QSARs analyses are reported in Tables 7–14.
Table 7 shows the predictions relating to the mutagenicity. The models gave
homogeneous and consistent results. Only exceptions are the predictions of
Toxsuite on HBCDD and Methylisothiazolinone which are in contrast with the
predictions of other models and with experimental data. Moreover, no predictions
are provided by Lazar for Isothiazolinones due to the absence of not enough similar
compounds in the training dataset.
Table 8 summarizes the carcinogenicity predictions. The models gave overall
consensual results. It is important that the different values from Toxtree models
reflect the capabilities of the models to provide prediction for non-genotoxic
(Toxtree 1) and genotoxic carcinogenicity (Toxtree 2). Also Lazar is able to predict
carcinogenic potential on six systems, so differences in the results are due to the
difference on analyzed target biological models.
Results from the application of QSARs models for Developmental Toxicity are
reported in Table 9. CAESAR bold values indicate that descriptors for these
compounds have values outside the descriptor range for the compounds of the
training set, suggesting that predictions are not reliable. Focusing on reliable
results, obtained predictions are quite controversial underlining the need of more
models for this endpoint.
198 D. Baderna et al.

Table 7 Results from QSARs: mutagenicity
ID Compound T.E.S.T CAESAR ToxSuite Lazar Experimental
1 PFOS No No Negative Negative
2 PFOA No No Negative Negative
3 NPAA No No Negative Negative
4 HBCDD No No Positive Negative Negative
5 Tridosan No No Negative Negative
6 DEI-P No No Negative Negative Negative
7 BDE99 No No Negative Negative
8 BDE100 No No Negative Negative
9 Decabromodiphenylether No No Negative Negative Negative
10 TPP No No Negative Negative Negative
11 NPE No No Negative Negative
12 BPA No No Negative Negative Negative
13 Kathon CG 5243 Yes Yes Positive – Positive
14 Methylisothiazolinone No No Positive –

Table 8 Results from QSARs: carcinogenicity
ToxTree ToxTree Lazar Lazar Lazar Lazar Lazar Lazar
ID CAESAR (1) (2) (1) (2) (3) (4) (5) (6)
1 No No No No No No No – No
2 No No No No No No Yes No No
3 No No No No No No No No No
4 No Yes No Yes Yes Yes – – –
5 No Yes No Yes Yes Yes Yes No No
6 No No No No No No Yes No No
7 No Yes No Yes – Yes Yes No No
8 No Yes No Yes – Yes Yes No No
9 No Yes No Yes Yes Yes Yes No No
10 No No No No No Yes No No No
11 No No No No No No Yes No No
12 No No No No No No Yes No No
13 Yes No Yes – – – No Yes –
14 No No Yes – – – – Yes –

Table 10 includes the results for skin irritation. No clear results have been
obtained. All models are in agreement only for the absence of irritative potential
of BDE 100. Multiple results from ToxTree are due to the five different alerts used
by the model (Schiff base formation, SNAr, Acyl transfer agent, skin sensitization,
and Michael acceptor). A global evaluation of ToxTree data could suggest that all
the analyzed compounds are not able to induce skin sensitization. These predictions
are in clear contrast with that obtained by applying CAESAR and in partial
agreement with the results of Toxsuite.
Results from the application of models for BCF in fish (LogBCF) are reported in
Table 11 with some comparison experimental values from models training set. Bold
Toxicological Characterization of Waste-Related Products Using Alternative. . . 199

Table 9 Results from QSARs: developmental toxicity
ID Compound T.E.S.T CAESAR
1 PFOS No No
2 PFOA Yes No
3 NPAA Yes No
4 HBCDD Yes Yes
5 Triclosan Yes No
6 DEHP Yes No
7 BDE99 Yes No
8 BDE100 Yes No
9 Decabromodiphenylether Yes No
10 TPP Yes No
11 NPE No No
12 BPA Yes No
13 Kathon CG 5243 Yes Yes
14 Methylisothiazolinone Yes No

Table 10 Results from QSARs: skin irritation
ID CAESAR ToxTree (1) ToxTree (2) ToxTree (3) ToxTree (4) ToxTree (5) ToxSuite
1 Inactive No No No No No Yes
2 Active No No No No No Yes
3 Active No No No No No Yes
4 Inactive No No No Yes No Yes
5 Active No No No No No No
6 Active No No No No No No
7 Inactive No Yes No Yes No No
8 Inactive No No No No No No
9 Active No Yes No Yes No No
10 Active No No No No No No
11 Active No No No No No No
12 Active No No No No No No
13 Active No No No Yes No No
14 Active No No No Yes Yes No

values from CAESAR indicate the presence of chemical features in the compound
(for example O linked to Ar and 3 Br/Cl linked to Ar or 10 F atoms in the molecule)
that might be associated with a lower reliability of the predicted value. Generally,
the predicted data have different levels of concordance. Evaluations for six
compounds (5, 10, 11, 12, 13, and 14) present a high degree of agreement while
the predictions for the other compounds are quite variable. It is important to
underline that in most cases the analyzed BCF model are conservative if compared
to the experimental data: predicted values are higher than experimental ones
resulting in overestimated bioconcentration potential. Moreover, it is interesting
that also experimental values present a high degree of variability.
200 D. Baderna et al.

Table 11 Results from QSARs: BCF
ID T.E.S.T CAESAR EOOSAR Experimental
1 3.12 1.7 0.5 3.73 –
2 2.54 2.53 0.5 3.12 –
3 1.37 2.09 1 – –
4 2.19 1.59 3.76 – –
5 2.58 2.71 2.808 1.67 1.7171
6 1.36 1.51 3.234 1.99 2.7694
7 3.29 1.94 4.18 – –
8 34 1.94 3.801 – –
9 2.07 1.02 1.62 1.2 3.38
10 2.14 2.12 1.871 2.48 2.281
11 2.19 2.89 2.093 2.55 2.58
12 1.76 1.97 1.858 1.39 1.8415
13 0.86 0.08 0.5 – –
14 0.46 0.06 0.5 – –

Table 12 Results from QSARs: 48 h LC50 Daphnia
ID Compound T.E.S.T ECOSAR ToxSuite Experimental
1 PFOS N/A 20.094 0.096 –
2 PFOA N/A 9.114 1.6 –
3 NPAA 2.57 0.954 8.5 –
4 HBCDD 1.65 0.006 7 –
5 Tridosan 0.38 0.991 0.37 –
6 DEHP 1.44 0.00147 10 11 –
7 BDE99 0.0217 0.006 0.14 –
8 BDE100 0.0569 0.006 0.14 –
9 Decabromodiphenylether 0.0571 0.00000236 0.00087 –
10 TPP 0.0719 1.042 0.0014 1
11 NPE 1.84 0.067 1.3 0.38 –
12 BPA 3.86 5.039 1.6 3.5 12.81
13 Kathon CG 5243 7.53 4787.144 14 –
14 Methylisothiazolinone 13.69 9060.711 22 –

The evaluation for aquatic toxicity on daphnids and fish is reported in Tables 12
and 13. Bold values indicate that compounds are out of the model applicability
domain (ECOSAR) or that the prediction is not reliable. ECOSAR and ToxSuite are
able to predict all the selected compounds while T.E.S.T. fails in prediction for the
daphnia toxicity of perfluorinated compounds (PFOS and PFOA). Tables 12 and 13
include also a limited number of experimental results provided by the model
training dataset (some data are extracted from USEPA Ecotox database). Predicted
results are in agreement for five compounds only (2, 3, 5, 13 and 14) for both
endpoints while the predictions for the other compounds are highly variable.
Toxicological Characterization of Waste-Related Products Using Alternative. . . 201

Table 13 Results from QSARs: 96 h LC50 fathead minnow
ID Compound T.E.S.T EOOSAR ToxSuite Experimental
1 PFOS 30.88 24.648 16 –
2 PFOA 28.2 10.662 130 –
3 NPAA 1.23 0.964 0.36 –
4 HBODD 0.21 0.004 0.00013 –
5 Tridosan 0.31 1.244 0.24 0.32 –
6 DEHP 0.0474 0.00117 0.43 16 –
7 BDE99 0.1 0.005 0.0024 –
8 BDE 100 0.0434 0.005 0.0043 –
9 Decabeomodiphenylether 0.00157 0.00000094 0.000000097 –
10 TPP 0.79 1.303 2.4 0.88 0.93
11 NFE 0.37 0.072 0.13 0.27
12 EPA 3.15 7.16 2.6 4.6 4.65
13 Kathon CG 5243 31.18 11008.46 94 –
14 Methylisothiazolinone 101.55 22113531 330 –

Table 14 Results from QSARs: Oral Rat LC50 (mg/kg b.w.)
ID Compound T.E.S.T ToxSuite Experimental
1 PFOS 238.47 1500
2 PFOA 225.47 420 430
3 NPAA 3924.02 7900
4 HBCDD 1908.39 850
5 Triclosan 65.76 2800 3700 3695.8
6 DEHP 37293.36 27000 30000
7 BDE99 581.16 2200 5000
8 BDE100 761.76 2600
9 Decabromodiphenylether 660.5 1500
10 TPP 1070.28 2700 3500 3496.37
11 NPE 2021.42 1900 1620 1618.8
12 BPA 3147.1 1900 3250 3247.32
13 Kathon CG 5243 680.71 590
14 Methylisothiazolinone 2868.62 580

Focusing on compounds with experimental data, we can underline that
– T.E.S.T. and ToxSuite are very conservative on prediction of aquatic toxicity;
– ECOSAR often underestimates values for daphnids and fish.
Results for the prediction of oral toxicity on rat are shown in Table 14. Bold
values indicated that prediction is not reliable. Table includes also a limited number
of experimental results provided by the model training dataset (some data are
extracted from ChemID database). Globally, values show a high degree of concur-
rence. The only exceptions are the predictions of triclosan and methylisothia-
zolinone toxicity: for triclosan, prediction made by T.E.S.T. is more conservative
than ToxSuite and experimental values while for methylisothiazolinone predicted
values from T.E.S.T and ToxSuite are variable.
202 D. Baderna et al.

5 Conclusions

This chapter describes some examples of application of alternative methods for the
study and characterization of the toxicity of some compounds of environmental
significance.
Among the possible techniques, in vitro assays and QSARs models are the most
relevant ones. Both tools have advantages and disadvantages which could be offset
by the integration of different approaches.
The investigation on leachate shown in the first paragraph suggests that, focusing
on risk assessment, chemical characterization alone is not sufficient to understand
the overall toxicity of conventional and unconventional environmental matrices.
Furthermore, risk assessment of complex mixtures, which is traditionally based on
chemical analyses of specific compounds, is not sufficiently developed to take into
account interactions among chemicals in the complex mixtures. A possible solution
is the use of bioassays (on simplified models like daphnids, algae, and worms) and
in vitro cell models which can integrate the biological effects of all mixture, in
contrast to chemical analyses.
The second example focused on the evaluation of carcinogenic potential of
PFCs. This property is one of the most important endpoint for hazard and risk
assessment of chemicals and pharmaceuticals in humans. Traditionally, this inves-
tigation requires time and money efforts because the standard approach to assess
carcinogenicity at a regulatory level is the 2-year bioassay in rodents. Highlights
from the revision underline that QSARs models and the BALB/c 3T3 in vitro CTA
could be very useful in reducing the number of compounds (and doses) which
should be tested for the screening of the carcinogenic potential. These results in a
significant reduction of animal consume which can be translated in both economic
and temporal saving.
Finally, results reported in the third part from evaluation of Riskcycle
compounds of concern suggest that the use of different QSARs models for the
same endpoint is a good practice to reduce the variability of the response.
Clearly, for some endpoints the models are more reliable. This is due to the
higher number of compounds available to build up the model and to the complexity
of the toxicological process which is modeled. Thus, for instance, models for
genotoxicity can refer to many thousands of chemicals with experimental values,
and the process is relatively simple. Conversely, reproductive toxicity is a much
more complex endpoint and the number of chemicals with experimental data is
limited (a few hundreds).

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LCA Case Study on Printed Matter

Henrik Fred Larsen

Abstract Previous product life cycle assessments (LCAs) on offset printed
matter all point at paper as the overall dominating contributor to the impacts from
the life cycle of this product category. The dominating role of paper is primarily
founded in the energy-related impact categories: global warming, acidification and
eutrophication. These former studies focus on impacts related to energy and the
chemical-related impact categories, comprising ecotoxicity and human toxicity, are
not included at all or only to a limited degree. In this chapter we present a newer
case study that includes these chemical-related impact categories by making use of
knowledge about emissions from the printing industry combined with knowledge
about the composition of the printing materials used during the production of offset
printed matter. The results show that the relative importance of the paper-related
energy consumption is significantly reduced when chemical emissions combined
with toxicity-related impact categories are included in the impact assessment. By
including results from a survey on the presence of hazardous chemicals in the
Danish printing industry, some of the potential additives/impurities that may appear
in the recycled paper are identified.

Keywords Additives, Chemicals, Impurities, Life cycle assessment (LCA), Paper,
Printing industry, Recycling

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
2 Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
2.1 LCA Case Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
3 Results of the LCA Case Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212

H.F. Larsen (*)
Research and Development, Road Directorate, Guldalderen 12, 2640 Hedehusene, Denmark
e-mail: hfl@vd.dk

B. Bilitewski et al. (eds.), Global Risk-Based Management of Chemical Additives II: 207
Risk-Based Assessment and Management Strategies, Hdb Env Chem (2013) 23: 207–222,
DOI 10.1007/698_2012_200, # Springer-Verlag Berlin Heidelberg 2012,
Published online: 24 November 2012
208 H.F. Larsen

4 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
4.1 Coverage of Chemical Emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
4.2 Potential Contributing Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
5 Research Needs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219

Abbreviations and Symbols

AOX Adsorbable organic halides
APE Alkylphenol ethoxylates
BPA Bisphenol A
CMR Carcinogenic, mutagenic and reprotoxic
COD Chemical oxygen demand
DTU Technical University of Denmark
ECHA European Chemicals Agency
EDS Endocrine-disrupting substances
eqv Equivalents
EU European Union
FP7 EU Seventh Framework Programme
ILCD The International Reference Life Cycle Data System
LAS Linear alkyl benzene sulphonates
LCA Life cycle assessment
LCI Life cycle inventory
LCIA Life cycle impact assessment
MSDS Material safety data sheets
NMVOC Non-methane volatile organic compounds
NPE Nonylphenol ethoxylates
PBT Persistent, bioaccumulative and toxic
PE Person-equivalents
PET Person-equivalents targeted
REACH Registration Evaluation, Authorisation and Restriction of Chemicals
SVHC Substances of very high concern
TOC Total organic carbon
VOC Volatile organic carbon
vPvB Very persistent and very bioaccumulative
WWTP Wastewater treatment plant
LCA Case Study on Printed Matter 209

1 Introduction

Until recently only a few life cycle assessment (LCA) studies [1–7] have been
done on printed matter, and most of them focus on energy consumption. However,
one of the newer and most comprehensive case studies [8, 9] actually includes
toxic impacts from chemical emissions – mostly printing chemicals like printing
ink and glue of which some components may accumulate in recycled paper.
Though recycling is included in this case study, there is, however, no special
focus on the additives/impurities in the recycled paper. Anyway, the study shows
that potential toxic impacts from the production and use of chemicals like
pigments, solvents, metals, AOX and biocides may play a very important role in
the LCA impact profile of printed matter. This chapter deals with LCA on printed
matter and focuses on the potential importance of chemical emissions, including
additives/impurities, for the LCA impact profile. Highly problematic additives/
chemicals that might stay/accumulate in the paper when recycled are addressed.
The main part of the research reported here is based on two studies performed
by the author, i.e. an LCA on printed matter [8, 9] and a Danish printing industry
substitution project including a survey on occurrence of hazardous substances
[10]. In Fig. 1 the life cycle of printed matter is illustrated by the cycle of the main
raw material paper.

2 Methodology

The method used in the LCA case study on printed matter [8, 9] is described in
Sect. 2.1. As regards general LCA methodology it is described in [34]; however,
methodology on life cycle impact assessment (LCIA) is further detailed below in
Sect. 2.1. Regarding the substitution project [10] the description of the method used
and the main results are part of the chapter “Case Study on Printed Matter in
Denmark” in Volume I of “Global Risk-Based Management of Chemical
Additives” [11]. Results from the substitution project [10] are only included here
to the degree relevant for the LCA of printed matter.

2.1 LCA Case Study

The goal of the LCA case study on printed matter [8] was to identify the distribution
of potential environmental impacts (hot spots) and resource consumption during the
life cycle of generic sheet fed offset printed matter produced at a European model
printing house. The functional unit is 1 ton of sheet fed offset printed matter (books,
pamphlets, brochures, etc.).
210 H.F. Larsen

Fig. 1 Life cycle of printed matter – focus on paper

The scope of the case study is depicted in Fig. 2. In the inventory, average data
on emissions and consumptions, typically based on 5–10 data points (depending on
the parameter) from a total of 71 Danish and Swedish printing houses and European
literature values, are used (foreground data). For the upstream and downstream
emissions and consumptions (background data), inventory data from databases like
“EDIP LCV tool” [12] and literature like BUWAL [13] and data from Swedish
paper mills [14] have been used. In the main scenario, it is assumed that 53% of the
paper is recycled and the rest incinerated (Danish situation in year 2000).
For the impact assessment, the midpoint method EDIP97 [15] was used, and the
following impact categories were included:
• Global warming
• Ozone depletion
• Acidification
• Nutrient enrichment
• Photochemical ozone formation
• Chronic human toxicity via water
• Chronic human toxicity via soil
• Chronic ecotoxicity in water
• Chronic ecotoxicity in soil
• Acute human toxicity via air
• Acute ecotoxicity in water
• Hazardous waste
• Nuclear waste
• Slag and ashes
• Bulk waste
• Resource consumption
LCA Case Study on Printed Matter 211

System boundary

Forestry Agriculture Extrac. and Excavation Extraction Excavation Extraction Extraction
refining of and refining and refining of of of silver
oil of Al of oil minerals bromide

Produc. Produc. of Produc. of Produc. Produc. of Produc. of Produc. Produc. Produc.
of pulp solvents and resin etc. of Al plate biocides of other of PET of film
detergents emulsion chemicals

Produc. of
pigments
Produc. of Produc. of Produc. of
Produc.
lacquer developer gumming
of paper
and fixer agent
Produc. of
ink

Produc. of
glue Produc. of
fountain
solution

Materials
Production
Repro

Plate-
making

Printing

Finishing
and
cleaning
Production
Use
Use

Use
Disposal
Avoided produc. Recycling of Incineration Avoided produc.
of paper paper of paper of energy

Fig. 2 Scope of case study on printed matter

As focus in this chapter is on additives/chemicals and emissions, the impact
category on resource consumption is not included. Results regarding resource
depletion may be found in the case study report [8].
An average of the impact potentials for the four impact categories on chronic
(eco)toxicity, i.e. chronic human toxicity via water, chronic human toxicity via soil,
chronic ecotoxicity in water and chronic ecotoxicity in soil, is defined as the
common impact category “persistent toxicity” [16] and used when calculating
normalised and weighted results.
Besides the two steps classification and characterisation, which are mandatory
according to ISO 14042 [17], the LCIA in this case study also includes the optional
steps normalisation and valuation (weighting).
During classification the emissions mapped in the inventory are assigned to the
relevant impact categories, e.g. carbon dioxide and methane emissions are assigned
212 H.F. Larsen

to global warming, and the methane emission is also assigned to photochemical
ozone formation. Then during characterisation a total impact potential is calculated
for each impact category, by summing up the results of each assigned emission
quantity multiplied by its corresponding characterisation factor within that
impact category. The characterisation factor is a substance, emission and impact
category-specific factor expressing the potential impact on the environment or
humans of emitting 1 kg of the substance in question. For example, regarding
carbon dioxide (CO2) emissions, the characterisation factor is 1 kg CO2-equivalents
(eqv)/kg CO2 emitted to air, and for methane (CH4), being 25 times more potent, the
corresponding factor is 25 kg CO2-eqv/kg CH4 emitted to air, both as related to the
impact category on global warming.
The calculated impact potentials are normalised within each impact category in
order to give an impression of their relative magnitude. The normalisation is
achieved by dividing the case study impact potentials by reference information
on the background impact from society’s total activities, i.e. the total impact
potential in the reference region divided by the number of citizens in that region.
For example, for global warming, the reference information or normalisation
reference for the year 1990 is 8,700 kg CO2-eqv/person/year, meaning that in
1990, greenhouse gases equivalent to 8,700 kg CO2 were emitted to air, on average,
for each citizen worldwide. The normalisation reference therefore represents the
annual impact of an average person. The normalised results are hereby expressed in
units of person-equivalents (PE).
The weighting factors for the individual impact categories are based on the
Danish political targets for the reduction of impact within regional and local impact
categories (e.g. ecotoxicity, acidification), whereas weighting of the global impact
categories (global warming and ozone depletion) is based on international
conventions and plans of action for reduction. The reference year is 1990 and the
target year is 2000, meaning that if the political target is to reduce the impact within
a certain impact category by 20% during that period, the weighting factor becomes
1.3 (1/(1  0.2) ¼ 1.3). The weighted normalised impact potentials are simply
calculated by multiplying the normalised impact potentials by the corresponding
weighting factor and expressed in targeted person-equivalents (PET).
For normalisation and weighting, the EDIP normalisation references regarding
the year 1990 and the EDIP weighting factors regarding the target year 2000 [16]
were used.
The case study was done in accordance with the ISO 14040 series [17–20] and
peer-reviewed. More details about the methodology used and the peer review may
be found in the work by Larsen et al. [8, 9].

3 Results of the LCA Case Study

The normalised and weighted impact profile for the case study is shown in Fig. 3.
The potential impacts are divided into nine phases/steps, mainly related to the
process steps at the model printing house and the paper production, incineration
LCA Case Study on Printed Matter 213

Paper prod. Human toxicity

Repro Ecotoxicity

Platemaking Persistent
toxicity
Printing
Photochemical
Finishing ozone

Cleaning Nutrient
enrichment
Energy at print
Acidification
Incineration
Global warming
Recovery

-200 -100 0 100 200 300 400 500 600 700 800

mPETWDK2000

Fig. 3 LCA impact profile on sheet fed offset printed matter (functional unit: 1 ton). Weighted
potential impact (milli-person-equivalents targeted), shown on the x-axis. Only seven impact
categories, i.e. human toxicity, ecotoxicity, etc. were shown here

and recycling (“recovery”), see Fig. 2. Only seven impact categories are shown, as
ozone depletion is insignificant and the four waste-related categories (bulk waste,
slag and ashes, etc.) are almost entirely related to paper production. Results
including all impact categories may be found in Larsen et al. [8, 9].
As is evident from Fig. 3, paper production contributes significantly (about 30%
of total) to the impact profile but is not at all dominating like in former studies
(60–80% of total) focusing on energy consumption and only including chemicals
and potential toxic impacts to a limited degree. If the toxicity-related impact
categories are excluded in this case study, the contribution from paper is increased
to 67% of total, which is at the level of the former studies.
The dominating potential impact in the impact profile (Fig. 3) is ecotoxicity,
i.e. acute ecotoxicity in water. For this category, the printing process accounts for
more than half and paper production below one-fifth of the total. This impact
category is dominated by contributions from emissions of tetradecane (printing
and cleaning at the production stage) and contribution from emissions of synthesis
chemicals (e.g. 3,3-dichlorobenzidine) at the synthesis of pigments (material stage).
Emission of strontium related to energy production (especially for production of
paper, i.e. heavy fuel oil for production of pulp) and emission of biocides at the
model printing house contribute less, but significantly.
The second most contributing impact category is persistent toxicity with the
cleaning step (e.g. emissions of hexane) at the printing house being the main
contributor followed by the printing step (e.g. emissions of isopropyl alcohol) and
paper production (e.g. emissions of strontium and mercury). For human toxicity
(acute human toxicity air), the contribution is minor and mainly related to energy
production, i.e. emissions of nitrogen oxides and sulphur dioxide.
214 H.F. Larsen

Global warming is the third most contributing impact category in the impact
profile shown in Fig. 3. It is highly dominated by emission appearing during energy
production, especially for production of paper (almost three-fourth of total), but
also from energy consumption at the model printing company (about one-fourth
of total). Nutrient enrichment and acidification contribute less but significantly
and are, as global warming, related to energy production. The impact category
photochemical ozone formation is dominated by contributions from printing (e.g.
emissions of isopropyl alcohol), paper production (e.g. energy-related VOC
emissions) and cleaning at the printing house (e.g. emissions of hexane).
If the avoided impacts from incineration of paper (i.e. avoided fossil fuel
consumption; “incineration” in Fig. 3) and the avoided impacts from recycling
paper (i.e. avoided production of virgin paper; “recovery” in Fig. 3) are allocated to
paper production, the contribution from paper to the total impact profile is reduced
significantly.
Even though recycling is included in this study (Fig. 3; “recovery”), there is no
special focus on the additives/impurities in the recycled paper. However, as
described above, the study shows that potential toxic impacts from the production
and use of chemicals like pigments, solvents, metals and biocides may play a very
significant role in the impact profile of printed matter. Focusing on chemicals, the
overall results for the printed matter impact profile, with avoided impacts from
incineration and recycling allocated to paper production, are described below
(in brackets: percentage contribution to the total normalised and weighted impact
potential):
• Emissions of ink residues like tetradecane and emissions of cleaning agents like
hexan and tetradecane, all during the printing process and cleaning (35%)
• Emissions of dichlorobenzidine, chloroaniline, cuprous chloride and more
during pigment production (17–20%)
• Emissions of heavy metals and AOX (as dichlorobenzene) during paper
production (>3%)
• Emissions of fountain chemicals (i.e. isopropyl alcohol) during the printing
process (6%)
• Emissions of biocides and hydroquinone from the repro- and plate-making
process (3%)

4 Discussion

The case study described here shows that emissions of chemicals, including
substances that might be considered as additives in the printed matter life cycle,
may contribute significantly to the LCA impact profile. In order to increase
the reliability of this result, confirmation, by use of newer and improved LCIA
methodology and updated LCI data for the background processes, are desirable.
Newer LCIA methodology has actually been used in other LCA studies on printed
LCA Case Study on Printed Matter 215

matter, but in all cases, the inclusion of chemical emissions and (eco)toxicity is
weak. Even a most recent Finnish LCA case study on different printing technologies
focuses on energy (and material) consumption and only includes toxicity-related
impact categories (human toxicity, terrestrial ecotoxicity and freshwater
ecotoxicity) for the case study on a photobook, i.e. electrophotography/digital
printing [21]. The LCIA method used is one of the newest, i.e. ReCiPe (www.lcia-
recipe.net (version November 2009)), but the study only includes cradle to consumer
(no “end of life” or recycling included). The resulting LCA impact profiles in this
Finnish case study shows dominance of the paper production together with the
packaging material (plastic) for the photobook and transport to the consumer.
Regarding the toxicity-related impact categories, only the normalised impact
potential for “freshwater ecotoxicity” is significant and mainly related to metal
emissions from plastic production. No other contribution from emissions of
chemicals used (e.g. additives) is mentioned in the study.

4.1 Coverage of Chemical Emissions

In the case study described in this chapter, a better coverage of the chemical-related
impact categories than in former has been aimed at by including characterisation
factors from recent work in other industry sectors and by calculating new ones for
chemical emissions expected to contribute significantly. Despite the fact that the
inventory of the production stage is much more detailed than that of the other
stages, even the composition of the raw materials used during the production stage
is based on simplifying assumptions, and some minor components have been
excluded due to lack of data.
The total number of chemical emissions to air included is about 100. Among
these, 33% are covered by characterisation factors for human toxicity and 26% are
covered by characterisation factors for ecotoxicity. The emissions from the material
stage and the disposal stage (mainly the former) include unspecific categories like
VOC, NMVOC and unspecified dust for which more specific information of actual
content is not available. In total, 48% of the emitted quantity (kg) is covered by
characterisation factors for human toxicity and 21% for the ecotoxicity part. If we
exclude the amount coming from some of the highest contributing emissions (SO2,
NOx, unspecified dust, calcium, Cl and suspended solids), for which at least the
main part typically does not contribute significantly to the potential ecotoxicity
impact, the coverage becomes 64% for the ecotoxicity impact category.
Regarding the total number of emissions to water, around 120 are included.
About 25% of the waterborne emissions are covered by characterisation factors for
human toxicity, and for ecotoxicity, the corresponding figure is 37% of the total
number. The waterborne emissions from the material and disposal stage also
include unspecific types like COD, TOC, VOC and suspended matter, for which
information of the actual content is not available. Only 3.1% of the total emitted
quantity (by weight) is covered by characterisation factors for human toxicity, and
216 H.F. Larsen

only 3.4% is covered for ecotoxicity. If we exclude the amount coming from
the highest contributing emissions (SO4, Tot-P, Na+, COD, calcium, Cl and
suspended solids), for which at least the main part typically does not contribute
significantly to the toxicity impact categories, the coverage becomes 48% for
human toxicity and 53% for the ecotoxicity part.
The main part of the specifically known individual emissions to water, which
are not included (i.e. characterisation factors lacking), consists of inorganic salts
(e.g. disodium silicate, sulphates), polymers (e.g. acrylates, modified phenol resin)
and acids/bases (e.g. NaOH, HCl). In general, these substances/mixtures have a low
toxicity and are not expected to contribute significantly to the toxicity impact
categories, if not emitted in high quantities. In the latter case they will typically
contribute only to acute ecotoxicity (e.g. reactive monomers from binders, acids or
bases causing low or high pH), and only if not treated in a wastewater treatment
plant (WWTP) before emission to the water recipient. Most of them have been
assessed in Larsen et al. [22–25] and Nielsen et al. [26], on the basis of hazard
assessments and/or generic risk assessments, regarding the potential effects if
emitted to a WWTP or directly to a water recipient.
Known emissions from the production stage, which are not covered by
characterisation factors and which may contribute significantly to the toxicity
impact categories, include emissions of components occurring in small quantities
in the raw materials (typically well below 5%) like siccatives (organic metal
compounds), softeners (phthalates), antioxidants (aromatics) and “wetteners”
(surfactants). Due to lack of readily available knowledge of their exact identity
and/or lack of readily available data on their inherent environmental properties, it
has not been possible to include them in the case study.

4.2 Potential Contributing Additives

As described in the chapter “Case Study on Printed Matter in Denmark” in Volume I
of “Global Risk-Based Management of Chemical Additives” [11], a substitution
project within the Danish printing industry was started up in 2006. A major part of
the work was to map the presence of chemicals which are potential candidates
for substitution (e.g. PBT, CMR, vPvB, EDS), especially related to the REACH
regulation [27]. The mapping comprised a combination of a literature study and an
investigation of the actual (2007) presence of candidate substances at 15 Danish
printing houses including the examination of almost 900 MSDSs (i.e. products).
Furthermore, a focused search in the Danish Product Register (http://arbejdstilsynet.
dk/en/engelsk/produktregistret.aspx) was included. About 30 of the substances,
actually found in the Danish printing industry, fulfil one or more of the criteria
(e.g. CMR, EDS) for the REACH Annex XIV candidate list [28], i.e. the candidate
list for the Authorisation list [29]. Eighteen of those substances appear as
components of printing inks and/or glues and therefore, in varying degrees, become
part of the printed matter when produced. When recycled, these substances may
therefore occur in the recycled paper as impurities.
LCA Case Study on Printed Matter 217

Table 1 Substances appearing as components of inks or glues and found in the Danish printing
industry. All substances meet one or more of the criteria (e.g. CMR, EDS) for the REACH Annex
XIV candidate list
REACH status
Name CAS No. Annex XIV criteria (June 2012)
Pigment yellow 34 (lead- 1344-37- Carc 1B, Rep 1A Authorisation list
chromate) 2
Pigment red 104 (lead- 12656- Carc 1B, Rep 1A Authorisation list
chromate) 85-8
Di(2-ethylhexyl)phthalate, 117-81-7 Rep 1B, EDS list (Cat 1) Authorisation list
DEHP
Dibutyl phthalate, DBP 84-74-2 Rep 1B, EDS list (Cat 1) Authorisation list
Benzyl butyl phthalate, BBP 85-68-7 Rep 1B, EDS list (Cat 1) Authorisation list
Trichloroethylene 79-01-6 Carc 1B Candidate list
Cobalt siccativesa (10124- (Carc 1B, Rep 1B) Candidate list
43-3)
Benzene 71-43-2 Carc 1A, Mut 1B Not listedb
2-Methylaziridine 75-55-8 Carc 1B Not listedb
Aziridine 151-56-4 Carc 1B, Mut 1B Not listedb
Propylene oxide 75-56-9 Carc 1B, Mut 1B Not listedb
2-Methoxy propylacetate 70657- Rep 1B Not listedb
70-4
Alkylphenol ethoxylates (25154- EDS list (Cat 1) Not listedb
52-3)
Octamethylcyclotetrasiloxane 556-67-2 EDS list (Cat 1), possible PBT/ Not listedb
(polydimethylsiloxane) (9016- vPvB substance
00-6)
Bisphenol A 80-05-7 EDS list (Cat 1) Not listedb
Resorcinol 108-46-3 EDS list (Cat 1) Not listedb
Styrene 100-42-5 EDS list (Cat 1) Not listedb
Decamethylcyclopentasiloxane 541-02-6 Possible PBT/vPvB substance Not listedb
a
Possible content of soluble cobalt(II) salts. Cobalt(II) sulphate, cobalt dichloride, cobalt(II)
carbonate, cobalt(II) dinitrate and cobalt(II) diacetate all appear on the recently updated
REACH Annex XIV candidate list [28]. IARC classifies all soluble cobalt(II) salts as possible
carcinogenic, i.e. group 2B (http://monographs.iarc.fr/ENG/Monographs/vol86/mono86.pdf)
b
Meaning not listed on the Authorisation list nor on its candidate list

The 18 substances are shown in Table 1. Five of these substances are now
(June 2012) included in Annex XIV (Authorisation list) [29]. These substances
are the lead-chromate pigments, pigment yellow 34 and pigment red 104, and the
phthalates DEHP, DBP and BBP, which all are used as components/additives in
some printing inks. As evident from Table 1, cobalt(II) salts and trichloroethylene
appear on the Annex XIV candidate list [28], and they are also used as additives in
some printing inks. ECHA has recommended in its third recommendation [30] to
put these two substances on the Authorisation list [29]. Besides these seven
substances of very high concern (SVHC substances) appearing on either the
Authorisation list or its candidate list, 11 other substances that meet one or more
of the criteria for the candidate list are shown in Table 1. These substances are also
218 H.F. Larsen

highly problematic and have the potential to follow the substrate, i.e. paper, when
recycled. Furthermore, it may be relevant, here, to mention that 26 hydrocarbon
mixtures, most probably containing hazardous single substances (e.g. hexane,
heptane, naphthalene) were also found in the Danish printing industry. Many of
these are used as components in printing inks (and cleaning agents) and therefore
may follow the printed substrate when recycled.
Actually, according to newer German investigations [31], dibutyl phthalate and
mineral oil components have been found in recycled paper used for food packaging,
giving rise to serious concern about potential human exposure. Also bisphenol A,
DEHP and alkylphenol ethoxylates have recently been found in recycled paper-
based food packaging on the Italian market [32].

5 Research Needs

In order to improve the comprehensiveness of the basis for the assessment,
including the coverage of chemical emissions, future LCA case studies on printed
matter need to include at least the following issues:
• Ink component (and their precursors) production: siccatives, antioxidants,
pigments, dyes, etc.
• Water emissions from paper production: softeners (BPA), other phenolic
compounds (NPE, APE), other surfactants (LAS), biocides (benzothiazoler,
dibromo compounds), wood extractions (terpenoids, resin acids) and more
• Recycling of paper: fate of paper chemicals, ink chemicals, glue chemicals, etc.
• Treatment of chemical waste: fate of (hazardous) waste from printing (ink waste,
used cleaning agents, used rinsing water, etc.) and from recycling of paper
(sludge from repulping)
The case study described here, though being the far most comprehensive on
chemical emissions and focus on toxicity-related impact categories, is a relatively
old study, and LCIA methodology has been extended and improved since it was
performed. Furthermore, it is always good to test the robustness of LCA results by
including different LCIA methods and different weighting principles. Therefore,
with the aim of trying to confirm the overall case study results and increase its
reliability, an updated LCA with especially improved background inventory data
and use of improved and different LCIA methodology is recommended. Actually,
in the ongoing (2012) EU FP7 research project LC-Impact (www.lc-impact.eu), an
improved and updated version, of the database used for the LCA case study shown
in this chapter, is going to be the basis for a new printed matter case study including
the involvement of ILCD-recommended LCIA methodology like USEtox [33]
for the toxicity-related impact categories.
LCA Case Study on Printed Matter 219

6 Conclusion

The case study presented here shows that chemical emissions may play a significant
role in the LCA impact profile of printed matter. Some of the chemicals related to
these emissions, like pigments and certain solvents, may be considered as additives
in the life cycle of printed matter. A survey in the Danish printing industry shows
occurrence of SVHC, and many of these, e.g. lead-chromate-based pigments and a
number of phthalates, are components of printing inks or glues that remain on the
paper when the printed matter is produced. They therefore have the potential of
becoming part of the recycled paper. Actually, some of these substances have been
found in food packaging based on recycled paper in recent German and Italian
studies. It might be that these additives/impurities contribute significantly to the
printed matter/paper LCA impact profile due to direct human exposure during the
use stage or emissions to the environment during the processing of the recycled
paper. However, this issue still needs to be investigated.

Acknowledgement Being part of the coordination action “RISKCYCLE” (Risk-based manage-
ment of chemicals and products in a circular economy at a global scale), this study is partly funded by
the 7th Framework Programme of the European Community (grant agreement no. FP7–226552). The
two main projects included, i.e. the case study on offset printed matter and the substitution
project, were financed by the Danish Environmental Protection Agency supplemented by in-kind
contributions from the industry partners.

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LCA Case Study Cushion Vinyl Floor Covering
and DEHP
Environmental Impacts of Use and Recycling
of Additives (DEHP) in Products

Lauran van Oers and Ester van der Voet

Abstract To illustrate the LCA method and its relevance for risk-based man-
agement of additives, an example is elaborated for a phthalate plasticizer, di
(2-ethylhexyl) phthalate (DEHP), as used in the application in cushion vinyl floor
covering. In LCA environmental impacts are estimated for the total of emissions,
not restricted to toxic effects and/or one substance (like DEHP). Furthermore
emissions relate to the cradle-to-grave chain of the additive application in cushion
vinyl floor covering. For the waste disposal of the EoL cushion vinyl floor covering
four different scenarios are elaborated: incineration; controlled landfill; uncon-
trolled land fill, assuming DEHP emission; and material recycling. Emissions of
DEHP are missing in the LC Inventory database. Therefore, additional estimates for
the emission of DEHP during production, use and waste disposal are based on
several MFA studies. The discussion mentions several limitations of the study.
Given these limitations, the scenario in which the EoL PVC waste is incinerated is
the environmentally worst option. The total weighted impacts for the other
scenarios are not far apart. However, the impact of incineration, with energy
recovery, is overestimated because burdens of waste incineration are completely
attributed to the cushion vinyl floor covering. The impact of uncontrolled landfill is
underestimated because the time horizon of DEHP leakage from the site is defined
rather short. The contribution of phthalates emissions to the impact score appears to
be small. An exception is the scenario in which the EoL waste is dumped on an
uncontrolled land fill site. In this case the fresh water ecotoxicity score becomes
substantial and is dominated by the emission of phthalate from the landfill site. This
will become even more apparent if a larger time horizon for DEHP leakage from the
landfill site is assumed.

L. van Oers (*) and E. van der Voet
Institute of Environmental Sciences, Leiden University, Einsteinweg 2, 2300 RA Leiden,
The Netherlands
e-mail: Oers@cml.leidenuniv.nl

B. Bilitewski et al. (eds.), Global Risk-Based Management of Chemical Additives II: 223
Risk-Based Assessment and Management Strategies, Hdb Env Chem (2013) 23: 223–244,
DOI 10.1007/698_2012_170, # Springer-Verlag Berlin Heidelberg 2012,
Published online: 10 July 2012
224 L. van Oers and E. van der Voet

Keywords Additive, Cushion Vinyl Floor Covering, DEHP, Life Cycle Analysis,
LCA, Plastic, Waste Treatment

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
2 Inventory Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
2.1 System Description and Flow Chart . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
2.2 Process Data for Incineration and Landfill . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
2.3 Process Data for Recycling, Mechanical Recycling of PVC and Allocation . . . . . . 227
3 Impact Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
4 Results, Environmental Impact Scores for the Use of Cushion Vinyl Floor Covering . . 229
4.1 Weighted Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
4.2 Normalized Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
5 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
5.1 Process Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
5.2 Impact Assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
5.3 Weighting Across Impact Categories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
6.1 General Conclusions Based on the Weighted Impact Scores . . . . . . . . . . . . . . . . . . . . . . . 240
6.2 Conclusions Based on the Normalized Toxicity Scores . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
6.3 Conclusions for the Additive DEHP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242

1 Introduction

To illustrate the LCA method [1] and its relevance for risk-based management of
additives, an example is elaborated for a phthalate plasticizer, di (2-ethylhexyl)
phthalate (DEHP), as used in the application in cushion vinyl floor covering.
This study deals with life cycle assessment of emissions related to the use of
additives in a plastic application. This means that environmental impacts are
estimated for the total of emissions, not restricted to toxic effects and/or one
substance (like DEHP). Furthermore emissions relate to the cradle-to-grave chain
of the additive application in cushion vinyl floor covering.

2 Inventory Analysis

2.1 System Description and Flow Chart

In this study the environmental impacts are calculated for the use of 1 m2 cushion
vinyl floor covering, with a lifetime of 15 years (in LCA terms called the functional
unit). Figure 1 shows the process flowchart for the production, use and waste
disposal of a cushion vinyl floor covering. Cushioned flooring is produced by
spread coating. The glass fibre is used as a substrate. Several layers, each with its
LCA Case Study Cushion Vinyl Floor Covering and DEHP 225

ground titanium other
PVC DEHP stabilizer glass fibre
limestone dioxide materials
production production production production
production production production

cushion vinyl
production

use of floor
covering
(lifetime 15
years)

collection and waste waste
recycling of disposal disposal
incineration of
vinyl vinyl landfill of vinyl

allocation allocation

Fig. 1 Flow chart of the production, use and waste disposal of cushion vinyl floor covering

Table 1 Composition of Cushion vinyl floor covering kg %
1 m2 cushion vinyl floor
covering [3] PVC 0.84 48.4
DEHP 0.51 29.1
Limestone 0.25 14.4
Stabilizer 0.050 2.9
Pigment 0.0050 0.3
Other materials 0.030 1.7
Glass fibre 0.055 3.2
Cushion vinyl floor covering 1.74 100

own function, are applied to the glass fibre. The product is so-called “cushion
flooring” since it typically involves at least one foam layer. The foamed layers
are mixtures of polyvinyl chloride, plasticizer, limestone, stabilizers, pigments and
some other additives [2–4].
The process description for the production of cushion vinyl floor covering is to a
large extent based on Potting and Blok [3]. In Table 1 the composition of 1 m2
cushion vinyl floor covering is given. In the plastic and additive market DEHP is
called a plastic additive, despite the large mass volume of DEHP used in CVFC. An
additional process for the production of DEHP is defined based on Potting and Blok
[3] and processes from the Ecoinvent database. Process descriptions of the back-
ground processes are based on the Ecoinvent database, version 2.2 [5]. Process
descriptions for the production of stabilizers and other materials are missing
226 L. van Oers and E. van der Voet

Table 2 DEHP emission factors to air and water based on MFA studies
Air Water Unit Reference
DEHP production 1.80E-06 4.50E-06 kg/kg [5]
DEHP industrial use 2.00E-04 6.00E-05 kg/kg [6]
End use floor covering 5.00E-04 0 kg/kg year [6]
Waste incineration 0 0 kg/kg [2, 6]
Waste landfill 0 0 kg/kg year [2, 6]

(marked grey in Fig. 1). In this study these materials are not further elaborated (see
Sect. 5). In the Ecoinvent database also emissions of DEHP are lacking. Therefore,
additional estimates (Table 2) for the emission of DEHP during production, use and
waste disposal are based on several Material Flow Accounting (MFA) studies
[2, 6–8].
The lifetime of the cushion vinyl floor covering is assumed to be 15 years. Indoor
emissions of DEHP during these 15 years are taken into account. The maintenance
of the floor is not taken into account.
For the waste disposal four different scenarios are elaborated:
• Incineration of the cushion vinyl floor covering
• Landfill of the cushion vinyl floor covering
• Landfill of the cushion vinyl floor covering, assuming additional DEHP
emission
• Material recycling of the cushion vinyl floor covering

2.2 Process Data for Incineration and Landfill

Emissions from incineration and landfill are based on material-specific inventories
for PVC sealing sheet, containing PVC, plasticizer, limestone and glass fibre. The
technologies described in the Ecoinvent database for incineration and landfill of
PVC should be considered as representative for a “high tech” society. For example,
the landfill represents a controlled site in which precaution measures are taken to
prevent direct leakage of toxic substances to surface and ground water. Further-
more, in a controlled landfill site the effluent from the site will be processed in a
sewage treatment plant and the sewage sludge will be incinerated. The process data
for landfill of PVC floor covering in the Ecoinvent database are inclusive the
burdens from the landfill, the waste water treatment of the effluent and the inciner-
ation of the sludge [9].
The material-specific burdens for the waste treatment are calculated by a
supporting spreadsheet of Ecoinvent. Necessary data for the calculation of the
burden are, e.g. element composition, water content, energy content, degradability
in landfill, etc. Note that the Ecoinvent waste management model estimates
emissions based on the element composition and some general characteristics of
the materials (like degradability). Detailed characteristics, like the mobility of
LCA Case Study Cushion Vinyl Floor Covering and DEHP 227

DEHP from PVC, are not taken into account. Therefore, additional assumptions are
made for the emission of DEHP from landfill of PVC.
In the MFA studies no direct emission of DEHP from waste incineration or landfill
to air or surface water are reported. For incineration it is assumed that DEHP is
decomposed into CO2 and H2O. For landfill it is assumed that DEHP is degraded
into CO2 and CH4 [10] or waste water (incl. DEHP) is treated in the WWTP [2, 6].
The above described landfill refers to a highly controlled landfill site with
emission precaution measures. However, in less controlled conditions DEHP
emissions might occur. Therefore, an additional assumption is made for emissions
of DEHP from uncontrolled landfill. The same yearly emission factor is used as for
the use phase of the floor covering, assuming a time period of 30 years instead of
15 years.

2.3 Process Data for Recycling, Mechanical Recycling of PVC
and Allocation

There are several options for the recycling of plastics (Delgado and Stenmark [11]):
– Mechanical recycling of materials (plastics)
– Chemical recycling of raw materials (monomers, etc.)
– Incineration, with energy recovery
Mechanical recycling is the preferred route for homogeneous and relatively
clean plastics waste streams. It is assumed that the cushion vinyl floor covering
will be mechanically recycled [11].1
In LCI databases no process data are found for the process of mechanical
recycling of PVC. Therefore, some rough assumptions have been made for the
definition of the process, like energy use, auxiliary material use and emissions
(including phthalate emissions).
The energy use and emissions are similar as in the process “production of
cushion vinyl floor covering”, but discarded cushion vinyl floor covering (waste)
is the economic inflow and the different materials (goods), like PVC, limestone,
glass fibre, etc., are the economic outflows.
The recycling of cushion vinyl floor covering is a multi-functional process with
the functions “treatment of waste” and “production of (several) materials”. The
“treatment of waste” is considered to be part of the primary system “cushion vinyl
floor covering”. The production of the materials is considered to be part of the

1
The building and construction plastics account only for 3% of overall collectable plastic waste in
Western Europe in 2002, of which about 8% is mechanically recycled within Europe on a regular
basis. However, the building and construction sector is an important end market for recycled
plastics from many sectors. Some 30% of overall recycled plastics are used in applications such as
insulation, fences and flooring.
228 L. van Oers and E. van der Voet

secondary system. This might be the secondary use of the materials for the
production of secondary cushion vinyl floor covering. The system boundary
between the primary and secondary system is situated within the recycling process.
As a proxy it is assumed that half of the process is allocated to the primary system
and half is allocated to the secondary system.

3 Impact Assessment

The aim of the Life Cycle Impact Assessment (LCIA) is to facilitate the interpreta-
tion of the results of the inventory analysis. The result of the inventory analysis is an
emission profile for each alternative system. In this study the emission profile is the
total of all emissions to air, water and soil from the grave-to-cradle chain for the use
of cushion vinyl floor covering, including the up chain processes, like electricity
production and the down chain processes, like the incineration and landfill of the
waste. Such an emission profile may consist of hundreds of emissions and
extractions. In LCA impact assessment the total of interventions (emissions,
extractions) of a process chain is evaluated in terms of environmental problems
(impact categories).
Basically the impact assessment involves the following steps:
• Characterization
• Normalization
• Weighting
Table 3 gives an overview of the environmental impact categories that are taken
into account in the environmental impact assessment according to the baseline
method that is recommended in the Dutch LCA Handbook [1]. The characterization
for toxicity is based on factors derived by the Usetox model [12]. The impact
categories “depletion of water” and “ionizing radiation” are not taken into account
because reliable characterization factors are not available.
ISO 14042 defines normalization as “calculation of the magnitude of indicator
results relative to reference information”. The main aim of normalizing the cate-
gory indicator results is to better understand the relative importance and magnitude
of these results for each product system under study. For the purpose of normaliza-
tion in LCA, Wegener Sleeswijk et al. [13] have made a comprehensive inventory
of extractions and emissions of substances for the world level in the year 2000. The
normalization in this project is based on these reference emissions and extractions.
As a result the normalized score of an impact category for the cushion vinyl floor
covering case is expressed as a fraction of the world problem.
Weighting is an optional step of impact assessment, in which the (normalized)
indicator results for each impact category assessed are assigned numerical factors
according to their relative importance, multiplied by these factors and possibly
aggregated. Weighting is based on value choices (e.g. monetary values, standards,
expert panel). A convenient name for the result of the weighting step is “weighting
LCA Case Study Cushion Vinyl Floor Covering and DEHP 229

Table 3 Impact categories, characterization and weighting factors
Baseline
Impact category characterization factor Weighting factor (%)
Climate change (global warming) GWP100 28
Stratospheric ozone depletion ODP1 5
Photo-oxidant formation POCP 6
(photochemical oxidation)
Human toxicity HTP1 21
Fresh water aquatic ecotoxicity FAETP1 19
Acidification AP 5
Eutrophication EP 8
Depletion of abiotic resources ADP 8
Total 100

result”, of which there is generally one for each alternative product system
analysed. Table 3 shows the weighting set that is used in this study to relatively
weight the environmental problems (impact categories) from the problem-oriented
approach. The weighting set is loosely based on the weighting sets for midpoint
impact categories as reported by Huppes and van Oers [14], a study funded by the
EC in which weighting sets are proposed to assess the overall EU27 impact based
on decoupling indicators.

4 Results, Environmental Impact Scores for the Use
of Cushion Vinyl Floor Covering

The environmental impact scores are calculated for four different sets of data. The
data sets differ in the type of waste treatment that is assumed for the end-of-life
waste:
– Use of cushion vinyl floor covering with incineration
– Use of cushion vinyl floor covering with landfill
– Use of cushion vinyl floor covering with landfill, incl. assumed DEHP emissions
– Use of cushion vinyl floor covering with recycling
Two versions for the waste treatment by landfill are elaborated. In one version
there are no emissions of DEHP from landfill sites. This assumption can be
considered as representative for a highly controlled landfill site. In a second version
of the waste treatment at an uncontrolled landfill site a DEHP emission is assumed.

4.1 Weighted Results

Figure 2 shows the weighted impact scores of the use of 1 m2 cushion vinyl floor
covering, broken down into environmental impact categories and Life Cycle stages.
230 L. van Oers and E. van der Voet

a 1,00E-13

9,00E-14

8,00E-14

7,00E-14
fraction of world problem

6,00E-14 other impacts
acidification
5,00E-14 photochemical oxidation
Freshwater ecotoxicity
4,00E-14 human toxicity
global warming
3,00E-14 depletion fossil fuels

2,00E-14

1,00E-14

0,00E+00
waste incinerated waste landfilled waste landfilled waste recycled
(incl DEHP emissions)

b 1,00E-13

9,00E-14

8,00E-14

7,00E-14
fraction of world problem

waste treatment
6,00E-14 emissions during use
assemblage cushion
vinyl floor covering
5,00E-14 titanium dioxide
glass fibre
limestone
4,00E-14
polyvinylchloride
DEHP
3,00E-14

2,00E-14

1,00E-14

0,00E+00
waste incinerated waste land filled waste land filled recycled
(incl DEHP emissions)

Fig. 2 Weighted impact scores of the use of 1 m2 cushion vinyl floor covering, broken down into
impacts (a) and Life Cycle stages (b)

Results are given for four different scenarios of waste treatment. Note that the
scores are the results of a weighting across different impacts categories.
According to these results, landfill of the waste, assuming no DEHP emissions, is
the most environmental friendly option, closely followed by the scenario assuming
material recycling of the end of life PVC waste. The worst option from an
environmental point of view is the incineration of the EoL PVC waste.
LCA Case Study Cushion Vinyl Floor Covering and DEHP 231

Figure 2a shows that for all scenarios the impact categories “global warming”
and depletion of fossil fuels contribute most to the total weighted score, respec-
tively, about 50% and 20–25%. The contribution of “global warming” for the
scenario with waste incineration is substantially higher, about 60% instead of
50%. In the waste treatment scenario “landfill with DEHP emission” also the
impact category “fresh water aquatic ecotoxicity” has a substantial contribution
to the total weighted impact score, about 15%. To a large extent this can be
attributed to the assumed emission of DEHP to water.
Figure 2b shows the contribution of the different Life Cycle stages of the use of
cushion vinyl floor covering to the weighted impact score. Most important pro-
cesses contributing to the weighted score are the production of DEHP and PVC,
about 30–35%. In the case of waste incineration also the waste treatment has a
substantial contribution, about 30%. Finally, the assemblage of cushion vinyl floor
covering has a contribution of about 20%. The emission of DEHP from the cushion
vinyl floor covering during use appears to have a negligible contribution.
According to these results, the production of the additive DEHP contributes to a
large extent to the total environmental impact score of the use of cushion vinyl floor
covering. Note that these impacts may be caused by substances other than DEHP!
Now the question is to which substances can the contributions be attributed?
Table 4 shows the contribution of the emitted substances from processes for the
weighted impact score. The emission of CO2 during incineration of EoL PVC and
other processes appears to have a large contribution. Also the ecotoxicity effect of
the emission of phthalate to water during landfill of EoL PVC appears to have a
substantial contribution.

4.2 Normalized Results

In the previous paragraph results are presented for the weighted impact score based
on all impact categories that are mentioned in Table 3. In this paragraph the focus is
on a selection of the impact categories. From a riskcycle perspective the toxicity
impacts are most relevant. Next to toxicity also global warming is presented
because it generally is considered an important problem. The results presented in
this paragraph are based on the normalized scores without a “value choice”
weighting between impact categories. Figure 3 shows the normalized scores for
the use of 1 m2 cushion vinyl floor covering for the impact categories “global
warming”, “human toxicity” and “aquatic ecotoxicity”.
Figure 3 shows that compared to “global warming” the cushion vinyl floor
covering has a relative low score for “human toxicity” and “aquatic ecotoxicity”.
In Figs. 4, 5 and 6 the normalized results are broken down into Life Cycle stages.
Tables 5 and 6 give the contribution of the emitted substances from processes for
the normalized impact scores for “human toxicity” and “aquatic ecotoxicity”.
The differences between the scenarios are completely explained by the
differences between the waste treatment options.
232

Table 4 Contribution of substance emissions to the weighted score for 1 m2 cushion vinyl floor covering (contributions <1% suppressed)
Contribution (%)
Landfill with
Process Elementary flow Category Incineration Landfill DEHP emissions Recycling
PVC flooring waste incineration Carbon dioxide [air] Global warming 21
Heat production from natural gas Carbon dioxide [air] Global warming 11 16 14 18
Polyvinylchloride production Carbon dioxide [air] Global warming 9 13 12 12
Cushion vinyl floor covering, to landfill Phthalate, dioctyl-[water] Freshwater ecotoxicity 9
Cushion vinyl production Ethene [air] Photochemical oxidation 4 6 5 5
Natural gas extraction Natural gas [resource] Resource depletion 2 6 5 6
Polyvinylchloride production Natural gas [resource] Resource depletion 2 4 3 3
Polyvinylchloride production Crude oil [resource] Resource depletion 2 3 3 3
Polyvinylchloride production Carbon dioxide [air] Global warming 2 3 2 2
Polyvinylchloride production Mercury [air] Human toxicity 1 1 1
Ethylene production Crude oil [resource] Resource depletion 1 2 2 2
Ethylene production Carbon dioxide [air] Global warming 2 2 2 2
Ethylene production Natural gas [resource] Resource depletion 1
Incineration residue, landfill Chromium VI [water] Freshwater ecotoxicity 2 2 2 2
Xylene production Carbon dioxide [air] Global warming 2 2 2 2
Xylene production Crude oil [resource] Resource depletion 1 1 1
Xylene production Natural gas [resource] Resource depletion 1
Heat production from heavy fuel oil Vanadium [air] Freshwater ecotoxicity 1 1 1
Recycling of cushion vinyl Ethene [air] Photochemical oxidation 3
floor covering
Total Total Total 59 65 66 66
L. van Oers and E. van der Voet
LCA Case Study Cushion Vinyl Floor Covering and DEHP 233

2,50E-13
global warming
human toxicity
aquatic eco toxicity
2,00E-13
fraction of world problem

1,50E-13

1,00E-13

5,00E-14

0,00E+00
waste incinerated waste landfilled waste landfilled waste recycled
(incl DEHP emissions)

Fig. 3 Normalized scores for the use of 1 m2 cushion vinyl floor covering for the impact
categories “global warming”, “human toxicity” and “aquatic ecotoxicity”

2,50E-13

2,00E-13
fraction of world problem

waste treatment
1,50E-13 emissions during use
assemblage cushion
vinyl floor covering
titanium dioxide production
1,00E-13 glass fibre production
limestone production
PVC production
DEHP production
5,00E-14

0,00E+00
waste incinerated waste landfilled waste landfilled waste recycled
(incl DEHP emissions)

Fig. 4 Normalized global warming impact scores of the use of 1 m2 cushion vinyl floor covering,
broken down into Life Cycle stages
234 L. van Oers and E. van der Voet

3,00E-14
fraction of world problem

2,00E-14 waste treatment
emissions during use
assemblage cushion
vinyl floor covering
titanium dioxide production
glass fibre production
1,00E-14 limestone production
PVC production
DEHP production

0,00E+00
waste incinerated waste landfilled waste landfilled waste recycled
(incl DEHP emissions)

Fig. 5 Normalized human toxicity impact scores of the use of 1 m2 cushion vinyl floor covering,
broken down into Life Cycle stages

7,00E-14

6,00E-14
fraction of world problem

5,00E-14
waste treatment
emissions during use
4,00E-14
assemblage cushion
vinyl floor covering
titanium dioxide production
3,00E-14
glass fibre production
limestone production
2,00E-14 PVC production
DEHP production

1,00E-14

0,00E+00
waste incinerated waste landfilled waste landfilled waste recycled
(incl DEHP emissions)

Fig. 6 Normalized aquatic ecotoxicity impact scores of the use of 1 m2 cushion vinyl floor
covering, broken down into Life Cycle stages

The waste treatment scenario with incineration has by far to the highest score for
global warming, followed by the scenario considering recycling. The impact scores
for the landfill scenarios are the lowest and, expectedly, the same for both scenarios.
The combustion of the EoL plastic will lead to large CO2 emissions. About 40% of
LCA Case Study Cushion Vinyl Floor Covering and DEHP 235

Table 5 Human toxicity, contribution of substance emissions to the normalized score for 1 m2
cushion vinyl floor covering (contributions <1% suppressed)
Contribution (%)
Landfill with
Process Elementary flow Incineration Landfill DEHP emissions Recycling
Polyvinylchloride Mercury [air] 26 48 47 47
production
Mercury production Mercury [air] 15
Sodium hydroxide Mercury [air] 15
production
Steel production, Mercury [air] 2
electric
Steel production, Mercury [air] 2 2 2
electric
Incineration residue, Chromium VI 4 8 8 8
landfill [water]
PVC flooring waste Chromium VI 2
incineration [water]
Glass fibre production Arsenic [air] 3 6 6 6
Incineration residue, Arsenic, ion 3 3 3
landfill [water]
PVC flooring waste Arsenic, ion 3
incineration [water]
Hard coal ash, landfill Arsenic, ion 1 1 1
[water]
Hard coal ash, landfill Arsenic, ion 1
[water]
Incineration residue, Arsenic, ion 2
landfill [water]
Glass fibre production Cadmium [air] 3 5 5 5
PVC flooring waste Lead [air] 1
incineration
Cushion vinyl floor Phthalate, 1
covering, to dioctyl-[air]
landfill (incl.
DEHP emissions)
Use of floor covering Phthalate, 1 1 1
(15 years) dioctyl-[air]
Cushion vinyl floor Phthalate, 1
covering, to dioctyl-
landfill (incl. [water]
DEHP emissions)
Zinc production, Zinc [air] 1 1 1 1
primary
Total Total 78 76 77 76

the global warming impact score can be attributed to the incineration of EoL PVC.
While emissions of greenhouse gases (GHG) in case of landfill of plastic will be
small because of the low degradability of the plastics. Emissions of GHG during
recycling are related to the energy consumption. About 10% of the global warming
impact score is caused by the energy consumed by the recycling process.
236 L. van Oers and E. van der Voet

Table 6 Aquatic eco toxicity, contribution of substance emissions to the normalized score for
1 m2 cushion vinyl floor covering (contributions <1% suppressed)
Contribution (%)
Landfill with
DEHP
Process Elementary flow Incineration Landfill emissions Recycling
Cushion vinyl floor Phthalate, 56
covering, to landfill dioctyl-
(incl. DEHP emissions) [water]
Cushion vinyl production Phthalate, 1 1
dioctyl-
[water]
Incineration residue, Chromium VI 21 29 12 29
landfill [water]
Heat production from Vanadium [air] 11 14 6 15
heavy fuel oil
Polyvinylchloride Zinc, ion [water] 9 12 5 13
production
PVC flooring waste Chromium VI 10
incineration [water]
Slag, unalloyed electr. Chromium VI 4 3 1 4
steel, to landfill [water]
Polyvinylchloride Copper, ion 3 5 2 5
production [water]
Incineration residue, Arsenic, ion 1 2 2
landfill [water]
PVC flooring waste Arsenic, ion 3
incineration [water]
Glass fibre production Arsenic [air] 2 2 2
Use of floor covering Phthalate, 1 2 2
(15 years) dioctyl-[air]
Polyvinylchloride sealing, Vanadium, ion 2
to sanitary landfill [water]
[CH]
PVC flooring waste Vanadium, ion 2
incineration [water]
Polyethylene waste Antimony 1
incineration [water]
Xylene production Nickel [air] 1 1
Total Total 67 73 83 72

Again, the waste treatment scenario with incineration has by far to the highest
score for human toxicity. The scores for the other scenarios are more or less the
same. The incineration of EoL PVC will lead to toxic emissions of metals (arsenic,
lead, chromium, see Table 5) causing human health effects. However, the most
important contribution to the human health effect is caused by the emission of
mercury in the upchain processes of the production of mercury and sodium hydroxide.
Sodium hydroxide is an auxiliary material in the waste incineration process. Mercury
LCA Case Study Cushion Vinyl Floor Covering and DEHP 237

cells are used for the electrolysis of NaCl into chlorine and sodium hydroxide. Toxic
emissions for human health in the other waste treatment processes seems to be
limited. Also for PVC production mercury appears to be the most dominant emis-
sion. Again this is caused by the use of mercury cells for the production of chlorine
which is used in PVC production. Finally, there are substantial contributions related
to the production of additives DEHP and glass fibre to the human toxicity score. Note
that these impacts may be caused by substances other than DEHP or glass fibre! In
fact Table 5 shows that DEHP emission of the production of DEHP has a negligible
contribution to the human toxicity score (contribution <1%). Of minor importance
are emissions of DEHP during use and landfill of the PVC (1–3%).
The comparison of aquatic ecotoxicity scores between the scenarios is
completely dominated by the assumed emission of DEHP from the (uncontrolled)
landfill site. If an emission is assumed the score for aquatic ecotoxicity will increase
substantially (a factor 2).

5 Discussion

5.1 Process Data

5.1.1 Lacking Process Data

Process data for the production of stabilizer and other materials are lacking. Also
possible emissions of these additives during use and waste disposal are missing.
According to Tukker et al. [2] and J€
onsson et al. [4] possible other materials might be:
– Stabilizer: Ba/Zn stabilizer, Ca/Zn stabilizer, SnS stabilizer, organotin (small
market)
– Other additives like flame retardants (BBP), etc.
– Other materials: PUR

5.1.2 Estimated Process Data on Waste Treatment

To estimate material-specific emissions from the waste treatment processes, landfill
and incineration, of EoL cushion vinyl floor covering a supporting spreadsheet of
Ecoinvent is used. The results will depend on the assumptions that are made in these
models. In this project these assumptions are not studied in detail. Necessary data
for the calculation of the burden are, e.g. element composition, water content,
energy content, degradability in landfill, etc. Note that the Ecoinvent waste
management model estimates emissions based on the element composition and
some general characteristics of the materials (like degradability). Detailed
238 L. van Oers and E. van der Voet

characteristics, like the mobility of DEHP from PVC are not taken into account.
Therefore, additional assumptions are made for the emission of DEHP from landfill
of PVC. Such additional assumptions might also be necessary for other substance
emissions, e.g. emission of methane from landfill sites, etc. For a detailed compari-
son of the waste treatment processes a more detailed analysis of the processes, the
characteristics of the disposed materials and the underlying models, is necessary.
Waste incineration with energy recovery is a common technique in Europe. The
process of waste incineration in the Ecoinvent database is also described as a multi-
functional process which delivers the function “waste treatment”, “electricity
production” and “heat production”. However, a more detailed study of the back-
ground report of the incineration processes shows that all the burdens are allocated
to the “waste treatment” function. So the production of electricity and heat are
without any burdens. This partly explains the high contribution of waste incinera-
tion to the total weighted impact score. If part of the burdens will be allocated to the
energy services, e.g. by using partitioning based on revenues (economic allocation),
the impact of the waste service which is attributed to the cushion vinyl floor
covering will decrease. As a result the total weighted impact score for the incinera-
tion scenario will decrease. For example, if economic allocation is used for
partitioning over the two different functions, assuming equal revenues for waste
treatment and energy production, the impacts related to the incineration of the EoL
plastic waste will be halved.
In the scenario for the controlled landfill site the treatment of effluent from the
site by sewage treatment and the incineration of the sludge are taken into account.
An additional scenario is made for an uncontrolled landfill site, assuming DEHP
emissions. However, in an uncontrolled landfill site not only DEHP will emit from
the site but also other toxic releases like heavy metals. So the results presented for
the uncontrolled landfill site are an underestimation. For a more realistic assessment
of impacts related to the uncontrolled landfill of PVC, additional estimates are
necessary for the emissions of (toxic) releases. As a consequence, the impact
assessment score for human and aquatic ecotoxicity for the uncontrolled landfill
site will increase. The relative contribution of DEHP to these scores will decrease
because also other emissions which are in the present assumptions are now lacking,
like heavy metals, will contribute to the score.
Furthermore, the emission of DEHP from the uncontrolled landfill site most
likely is underestimated. The estimate is based on the yearly emission factor that is
used for the indoor emission during the use of the floor covering. The time period of
the DEHP leakage from cushion vinyl floor covering at the landfill site is quite
arbitrarily set at 30 years. The emission from landfill site attributed to the functional
unit of the use of 1 m2 cushion vinyl floor covering will increase if the estimate is
based on a larger time period, e.g. 100 years. Therefore, given the fact that
landfilled waste will remain on the site for a long period of time the impacts of
toxic emissions from the uncontrolled landfill site most likely are underestimated.
LCA Case Study Cushion Vinyl Floor Covering and DEHP 239

5.1.3 Outdated Process Data

In the results the emissions of mercury appear to have a very substantial contribu-
tion for the human toxicity impact score. These emissions are caused by the
coproduction of chlorine and sodium hydroxide by electrolysis using a mercury
cell. However, this technique is phased out. Therefore, the process descriptions in
the Ecoinvent database do not represent up to date technology. In the Ecoinvent
database the process for PVC production, in which chlorine is used as one of the
compounds, is an aggregated processes based on, seemingly outdated, data from
PlasticsEurope. These outdated data also influence the impacts related to waste
treatment by incineration because sodium hydroxide is necessary for the waste
incineration process.

5.2 Impact Assessment

5.2.1 Dominance of Heavy Metals

In the LCIA community there is much discussion on the characterization of heavy
metals for toxicity. Due to large residence times in the environment, the characteri-
zation factors for heavy metals tend to dominate the impact scores for toxicity
impact categories. This might suppress the impacts of other relevant toxic
substances, like DEHP. For this reason the results are calculated using the charac-
terization factors derived by the Usetox model instead of the Uses model. Uses
model is the original baseline characterization model that is recommended in the
Dutch LCA Handbook [1].

5.2.2 Missing Pathways Human Toxicity

In Franco et al. [15] it is concluded that the characterization models, like EUSES
and ACC-human, underestimate human exposure to phthalate esters because they
consider only a few key pathways. It is not known whether the more relevant
pathways for phthalate esters are taken into account in the Usetox model?

5.2.3 Missing Pathways for Indoor Emissions During Use Phase

Emissions of DEHP during use of the cushion vinyl floor covering appear to have a
negligible contribution in the total weighted score. However, the assessment of the
impact of the DEHP emission on human health is based on a characterization model
that is developed for outdoor emissions, Usetox. The emission of DEHP during the
use phase of the floor covering is indoors and therefore fate and the human exposure
240 L. van Oers and E. van der Voet

will be different compared to an outdoor emission. It is very likely that indoor
emissions of DEHP will have a larger impact on human health effects than outdoor
emissions. In most LCAs effect on human health due to indoor emissions are not
considered in the total weighted impact score.
So the indoor emissions need a specific fate and exposure modelling. In Meijer
et al. [16, 17] a characterization model and characterization factors for indoor
emissions are presented. In the articles also indoor emissions of some building
materials are estimated and their effects are calculated. It is concluded that damage
effects of indoor emissions cannot be neglected.
However, although a characterization model is available for indoor emissions it
is still difficult to take into account these indoor emissions because for the interpre-
tation of the impact assessment also normalization data are desirable. For this a
world covering estimate of the indoor emissions of toxic substances is necessary.

5.3 Weighting Across Impact Categories

The contribution of different impact categories to the total weighted score by
definition depends on the weighting set that is used to weight across impact
categories. In the weighting set that is applied in this project (Table 3) relative
high weighting factors are given for the impact categories “global warming” (28)
and “human toxicity” (21). The weighting across impact categories are based on
subjective choices and therefore by definition a topic of discussion. Nevertheless, in
this project weighted impact scores are used to get an overall picture of the
environmental impacts for the different scenarios. Subsequently the focus is put
on the separate impact categories “human toxicity”, “aquatic ecotoxicity” and
“global warming”, avoiding the weighting.

6 Conclusion

6.1 General Conclusions Based on the Weighted Impact Scores

Given the system assumptions and characterization models that are used in this
project the scenario in which the EoL PVC waste is incinerated is the environmen-
tally worst option. The total weighted impacts for the other scenarios are not far
apart.
However, the assumptions of the present system have some important draw
backs. The impact of incineration, with energy recovery, is overestimated because
burdens of incineration are completely attributed to the waste treatment of cushion
vinyl floor covering while none is attributed to the production of energy, which is a
co-function of the waste incineration.
LCA Case Study Cushion Vinyl Floor Covering and DEHP 241

Furthermore, the impacts on toxicity scores for the uncontrolled landfill site are
most likely underestimated. The time period of DEHP leakage from the landfill site
is assumed to be rather short (set at 30 years whilst a larger period, e.g. 100 years,
seems more appropriate).
The impact to the total weighted score of the emission of DEHP during use of the
cushion vinyl floor covering is negligible.
The impact category “global warming” contributes most to the total environ-
mental impact score (60–50%).
The impact category “human toxicity” (based on USESTOX characterization
factors) has a small contribution to the total environmental impact score (about 5%).
Also the impact category “aquatic ecotoxicity” has a small contribution to the
total environmental impact score (about 8%), with an exception for the landfill
scenario with DEHP emission (about 17%). Emission of DEHP from an uncon-
trolled landfill site, the landfill scenario with DEHP emission, appears to have a
substantial contribution to the total weighted impact score.

6.2 Conclusions Based on the Normalized Toxicity Scores

The impact score for human toxicity appears to be relatively low compared to the
other environmental impacts. The contribution of phthalates to this impact score is
small. If incineration is assumed this contribution is less than 1%. The other
extreme, if landfill with DEHP emission is assumed, this contribution is 3%.
The impact score for fresh water ecotoxicity is relatively low compared to the
other environmental impacts for the cases incineration, landfill without DEHP
emissions and recycling.
Only in the case of landfill with DEHP emissions the contribution of phthalate
emissions to the freshwater ecotoxicity becomes dominant. In this case also the
fresh water ecotoxicity score is substantial compared to the other environmental
impact scores.

6.3 Conclusions for the Additive DEHP

For aquatic toxicity the landfill without leaching prevention is by far the worst
option, while the controlled landfill site is the best one, together with recycling. The
waste phase therefore is a crucial issue, and can be influenced to a large extent.
Secondly, DEHP is important in the life cycle of PVC flooring, both in the
production and the waste management phase. In the third place, emissions during
use, although included in the analysis, do not seem to be important in the life cycle.
For global warming the DEHP production contributes significantly to GHG
emissions. Also the waste phase seems to be important and can be influenced.
Incineration seems the worst option for waste treatment due to CO2 emissions from
242 L. van Oers and E. van der Voet

incinerated plastic. The two landfill options appear to be the best ones – in this case,
the least energy-intensive.
So from the point of view of additives, it seems that they may indeed contribute
significantly to life cycle impacts. The case study of PVC flooring shows that
additives contribute significantly, not just to toxicity impact due to DEHP emissions
but also to global warming due to GHG emissions along the Cradle-to-Grave chain
of the compound DEHP.

References

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Sleeswijk A, Suh S, Udo de Haes HA, de Bruijn H, van Duin R, Huijbregts MAJ (2002)
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study. Build Environ 32(3):245–255
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control of priority substances in Europe. Norwegian Institute for Air Research (NILU), Kjeller,
Norway. http://www.socopse.se/download/18.2f3a7b311a7c8064438000936916/Annexe+4.
+Deliverable++2+1.pdf
7. Lindeboom R (2009) An inventory and assessment of options for reducing emissions: DEHP.
SOCOPSE – source control of priority substances in Europe. http://www.socopse.se/down-
load/18.3cd20f1b1243376c1168000574/SR+DEHP.pdf
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Rydberg T, Tivander J, Öman A (2010) National inventory of emissions of additives from
plastic materials. Chemitecs report P4-D4. IVL, G€ oteborg, Sweden
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report no. 13. Ecoinvent, St-Gallen, Switzerland. http://www.ecoinvent.ch/
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1(4):93–116
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Normalisation in product life cycle assessment: an LCA of the global and European economic
systems in the year 2000. Sci Total Environ 390(1):227–240
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damage scores (10 pp). Int J Life Cycle Assess 10(6):383–392
Chemicals in Leather: International Trends
on Risk-Based Control and Management

Stefan Rydin

Abstract The leather sector is a traditional industry. This chapter will give an
overview of the use of chemicals in the leather sector and identify different types
and amounts of chemicals used in the different processes.
During recent years, there has been an increased focus on chemical substances
including additives in many different articles such as shoes and gloves. In particular
articles that come into contact with humans have been in focus. The concern
being that humans and the environment will be exposed to hazardous substances
from articles.
This chapter will give an overview of recent international trends and initiatives
regarding chemicals in leather and articles containing leather. That includes the
identification of chemicals in the produced leather that are common on restricted
substance lists and present ongoing recent initiatives to control the impact from
these chemicals including both legislative measures and initiatives from customers
such as international brands or purchasing sectors and different eco-labels.

Keywords Additives, Chemicals, Eco-label, Leather, Restricted substances,
Tanning

Contents
1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
2 Use of Chemicals in the Leather Sector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
3 Drivers for Chemical Management in Tanneries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
3.1 National Regulations and Laws . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
3.2 International Agreements and Regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
3.3 Eco-labels for Consumer Items . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
3.4 Manufacturers and Brands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255

S. Rydin (*)
Nordeconsult Sweden AB, Sofiaparken 3C, 222 41 Lund, Sweden
e-mail: stefan.rydin@nordeconsult.com

B. Bilitewski et al. (eds.), Global Risk-Based Management of Chemical Additives II: 245
Risk-Based Assessment and Management Strategies, Hdb Env Chem (2013) 23: 245–262,
DOI 10.1007/698_2012_201, # Springer-Verlag Berlin Heidelberg 2012,
Published online: 24 November 2012
246 S. Rydin

4 Restricted Chemicals with Relevance for the Leather Sector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
4.1 Aromatic Amines from Azo Dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
4.2 Pentachlorophenol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
4.3 Chlorinated Paraffins (SCCP, Short Chain) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
4.4 Chromium (VI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
4.5 Dimethyl Fumarate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
4.6 Nonylphenol Ethoxylate/Nonylphenol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
4.7 Other Chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261

Abbreviations

AOX Adsorbable organic halogen
APE Alkylphenol ethoxylates
BAT Best available techniques
BBP Benzyl butyl phthalate
BREF BAT reference document
COD Chemical oxygen demand
DBP Dibutyl phthalate
DEHP Bis(2-ethylhexyl) phthalate
DMF Dimethyl fumarate
EPA Environmental Protection Agency
EU European Union
GADSL Global automotive declarable substance list
IED Industrial Emissions Directive
LWG Leather Working Group
NGO Non-governmental organisation
NP Nonylphenol
NPE Nonylphenol ethoxylates
PCP Pentachlorophenol
PFOS Perfluorooctane sulfonates
POP Persistent organic chemicals
REACH Registration Evaluation, Authorisation and Restriction of Chemical
Substances (European Community Regulation on chemicals and their
safe use)
RSL Restricted substance lists
SCCP Short-chain chlorinated paraffins
SSEI Swedish Shoe Environmental Initiative
STWI Sweden Textile Water Initiative
SVHC Substance of very high concern
TCP Trichlorophenol
VOCs Volatile organic compounds
Chemicals in Leather: International Trends on Risk-Based Control and Management 247

1 Background

The leather industry is a traditional industrial sector. The industry uses both a high
variety and high amount of chemicals during the production of leather from raw
hides and skins.
Tanneries use around 2–3 kg of chemicals for every kilogram of leather that is
produced. It is not uncommon that a medium-sized tannery uses around 300–400
different chemicals in the production, and recent published data from a tannery
showed they were using around 350 different chemicals in the production [1]. It
should also be noted that less than 20% of the weight of the hides that will be
processed will actually end up as leather. The remaining part will become waste or
by-products. A typical mass balance from a tannery producing leather from bovine
hides is given in Fig. 1.
The production of raw hides and skins depends on the availability of raw
materials, which is regulated by animal population, offtake ratio and the weight
per hide and skin recovered. The availability of raw material depends therefore on
the meat consumption in the world. The main centres for raw hide/skin production
do not necessarily coincide with the major leather production centres. There is a
worldwide transport of salted hides/skins from areas with raw hide production to
areas with a tanning industry. Between the early 1980s and mid 1990s, a major part
of the world production was moved to the developing countries from the developed
countries. The developing countries produce around 64% of the number of hides,
and with respect to the sheepskins, developing countries account for about 65% of
the global number of skins produced. In particular, the tanning industry has
increased in size in the Far East and Latin America. The main producing country
of leather today is China followed by Italy, India and Brazil.
Europe is still the main market for leather products and leather produced in the
developing countries, e.g. Southeast Asia, may therefore end up on the European
market and to European consumers. Chemicals that are added during the production,
and which stay on/in the product, will hence be transported by the product to the final
markets, and there will be a chemical flow around the world through the transport of
leather and leather products containing chemicals. Since the tanning industry is a
chemically intensive industry, an efficient chemical management in tanneries is
necessary in order to minimise the overall use of chemicals and in particular also to
reduce the amount of hazardous chemicals used in order to minimise eventual health
effects on the consumer.
There are several initiatives and actions in order to control and stimulate a
more efficient chemical management in the tanning sector. The main incentives
are environmental legislations and customer requirements. The customer require-
ment can be expressed as either eco-labels or restriction substance lists (RSL)
of chemicals in the products developed by major brands or several industrial
groups.
248 S. Rydin

Fig. 1 Mass balance during leather production

2 Use of Chemicals in the Leather Sector

The amount of chemicals used varies significantly with the specification of the final
product, the types of hides and skins that are treated and the process chosen.
Figures for the consumption of chemicals can therefore only be given within a
broad range. The water content must also be taken into account when comparing
consumption figures. An example of a brief overview of the chemical consumption
is given in Table 1 [2].
The major parts of the chemicals that are use are inorganic bulk chemicals.
Around 20–50% of the chemicals that are added are inorganic standard chemicals.
The inorganic chemicals generally used are calcium hydroxide, sodium chloride,
sodium sulphide, acids, carbonates and sulphates. Besides the inorganic standard
chemicals, chromium sulphate is also widely used as a tanning agent, and the
consumption of chrome tanning agents is often around 80 kg/ton salted hides
(corresponding to around 15 kg chromium/ton salted raw hide).
Around 10–40% of the chemical consumption in a tannery is organic chemicals.
Examples of standard organic chemicals used are organic acids and their salts.
Besides the main process chemicals, a great variety of chemicals are used for
auxiliary process purposes. These auxiliary agents may demand special attention
because of the problem of reactivity, toxicity, persistence, bioaccumulation, mobility
and the generation of problematic metabolites. It is, therefore, important to know the
quantities used and their characteristics.
Globally, approximately 6.0 million tonnes of raw hides (on a wet salted basis) is
processed to leather [3]. In addition, around 650,000 tonnes of goat- and sheepskins
is processed to leather [3]. This indicates that globally around 3 million tonnes of
chemicals is used to produce leather. It is hence of importance that the chemical
Chemicals in Leather: International Trends on Risk-Based Control and Management 249

Table 1 Use of chemicals in the leather sector
Chemical Kg/ton salted raw hide
Standard chemicals, inorganic 215
Standard chemicals, organic 35
Enzyme preparations 7
Detergents 8
Biocides 1
Chrome tanning agents 80
Vegetable and synthetic tanning agents 40
Resins and dye assistants 10
Dyes 9
Fatliquoring agents 40
Waterproofing agents 2
Pigments 4
Finish chemicals 46
Organic solvents 24
Total 521

consumption is reduced as much as possible and that the use of hazardous
chemicals is avoided. The substitution of hazardous chemicals to less toxic
chemicals should have a high priority for the leather sector.
A practical problem faced by tanneries is that many chemical products are
proprietary products. Many suppliers do not specify the chemical composition of
the products, so tanneries may have to seek additional information from the
chemical suppliers in order to determine the environmental impact of the products
they use. Sometimes it is also difficult for tanneries to receive accurate information
also from the suppliers of the chemicals. Material safety data sheets generally
provide some data on the toxicity of the products to humans and environment,
and many tanneries use these as the sole source of information to determine the
environmental impact of a certain substance. It can be expected in the EU in the
future that tanneries will receive more detailed information about the substances
used because of the REACH legislation.

3 Drivers for Chemical Management in Tanneries

The chemicals that are used in the tanning sector will end up either in the leather
product, in the waste or will be discharged either to water, air or soil. There is
different legislation depending on if the chemical will end up in the product or if it
will end up in the environment. This chapter focuses on the drivers for avoiding or
restricting certain chemicals in the products.
There are basically two stakeholder groups involved in the development of
criteria for leather products or development of restricted substance lists. These
stakeholder groups are legislators (national regulations and laws and international
250 S. Rydin

agreements and regulations) and manufacturers/brands and eco-labels (global
brands, industrial sectors and several different types of eco-labels for consumer
items).

3.1 National Regulations and Laws

The relevant legislation for tanneries regarding the use of chemicals can be found
both in legislation regarding environmental permits for the industrial installations
which in some cases addresses substitution of chemicals. One example of this is the
EU Industrial Emissions Directive [4] which regulates emissions from industrial
installation within the EU. One key aspect in this directive is how problematic
chemicals should be substituted to more environmentally friendly alternatives
by tanneries.
The other type of legislation regulates the use of chemicals and also regulates the
content of some specific chemicals in the final products. As example, the European
chemical legislation REACH can be mentioned [5]. Annex XVII sets out the list of
restrictions on the manufacture, placing on the market and use of certain dangerous
chemical substances, mixtures and articles.
The different types of legislation are presented below.

3.1.1 Industrial Emissions Directive

The EU Directive on industrial emissions [4] which often is called IED was adopted
on 24 November 2010 (it was a result of merging seven different EU Directives
including the IPPC Directive into one directive). The directive regulates emissions
from large industrial installations within the EU. The directive was put into force on
6 January 2011 and should be implemented by all the 27 member states in the EU by
7 January 2013.
The directive sets out the main principles for the permitting and control of
industrial installations based on an integrated approach and the application of
best available techniques (BAT) which are the most effective techniques to achieve
a high level of environmental protection, taking into account the costs and benefits.
In order to have a common understanding of BAT within Europe, BAT reference
documents (BREF) are developed by the European Commission. These documents
describe what is considered to be the BAT at the different process stages. Under the
direction of the IPPC office in Seville, BREF documents are produced within
technical working groups (TWG) with the participation of industry, EU member
states and relevant organisations. The work on a BREF frequently takes several
years and results in a comprehensive document with detailed descriptions of
technical benchmarks for all parts of an industrial process. A BREF is revised
roughly every eighth year. There exist currently (2012) 35 BREF, and one of these
BREFs is one developed for the tanning industry (TAN BREF).
Chemicals in Leather: International Trends on Risk-Based Control and Management 251

The TAN BREF document is at the moment revised, but a new version is expected
to be adopted by the end of November 2012. The document contains information
about the leather industry in general, the leather industry in EU, conventional
technologies used, BAT and also emission levels which are possible to be achieved
by the use of BAT. The document includes information of substitution of chemicals
in the industry. However, the document does not specifically address human health
risks due to chemicals in the products since that subject is covered by other legislation
within the EU. However, the document gives guidance on use of alternative
chemicals as an alternative to the use of several problematic chemicals.
The TAN BREF document can be found on the homepage of the European IPPC
Bureau [3].

3.1.2 Legislation Concerning Chemicals

Each country has its own regulation and laws regarding chemicals. There are major
differences between different countries, and some countries have considerably
more regulations than other countries.
The chemical legislation in the European Union has been put together into one
EU Regulation which is the EU Regulation called REACH [5]. Since the legislation
is in the form of a regulation, it is mandatory for all 27 member states in
the European Union. It deals with the registration, evaluation, authorisation and
restriction of chemical substances. The law entered into force on 1 June 2007. The
main objective of REACH is to improve the protection of human health and the
environment through the better and earlier identification of intrinsic hazardous
properties of chemical substances. One of the main reasons for developing and
adopting the REACH Regulation was that a large number of substances have been
manufactured and placed on the market in Europe for many years, sometimes in
very high amounts, and yet there is insufficient information on the hazards that they
pose to human health and the environment.
Furthermore, the EU regularly produces and regularly updates the list of
substances of high concern, i.e. the SVHC list. The identification of a substance as
a SVHC and its inclusion in the candidate list is the first step of the authorization
procedure. The European Chemical Agency in Helsinki identifies from the candidate
list priority substances to be included in Annex XIV of REACH (the authorisation
list). The substances on the candidate list will most probably be liable to stricter
regulation in the future (authorisation/banning) which will stimulate the substitution
of these chemicals. Currently in June 2012, there are 84 substances included in the
candidate list. Examples of chemicals on the candidate list which may be relevant
for the leather industry are phenolphthalein, boric acid, cobalt dichloride, dichromate
(although not used by leather industry), phthalates (DEHP, DBP and BBP),
acrylamide and short-chain chlorinated paraffins.
Companies may have immediate legal obligations following such inclusion
which are linked to the listed substances on its own, in preparations and articles.
252 S. Rydin

Furthermore, many restriction lists and eco-labels will include chemicals on the
SVHC list in their restriction lists and criteria for eco-labels.
The restriction of chemicals has been included in Annex XVII of REACH. The
annex deals with the restriction of manufacture, placing on market and use of
certain dangerous substances, preparations and articles.
The EU Regulation restricts either
• The sale or manufacture within the EU of product formulations containing more
than certain amounts of chemical substances
• The presence of certain chemical substances in consumer goods
Other countries besides the EU also have introduced legislation regarding
chemicals in products although the EU is a key driver regarding environmental
legislation. For example, the Federal Agencies, EPA (Environmental Protection
Agency) and CPSC (Consumer Product Safety Commission), which control
regulations and guidelines at a national level in the USA, may be mentioned. In
addition, the individual states have their own regulations (e.g. California).
Japan has regulations for harmful substances, and the most relevant for the
leather industry is the Law 112 restricting harmful substances (e.g. formaldehyde)
in household products.
Furthermore, China has recently implemented a chemical legislation similar to
EU REACH, and the legislation is sometimes called the China REACH. The China
REACH came into force in 15 October 2010.

3.2 International Agreements and Regulations

There are several international treaties and agreements administrated by the United
Nations which limit specific chemicals.
One of the most known is the “Stockholm Convention of Persistent
Organic Pollutants (POPs)” which is signed by 151 countries [6]. The Stockholm
Convention, which was adopted in 2001 and entered into force in year 2004,
requires all parties to take measures to eliminate or reduce the release of POPs
into the environment.
POPs are organic chemical substances that resist biodegradation, are toxic to
both humans and wildlife and furthermore tend to accumulate in living tissues.
The convention includes currently 21 POP substances such as chlorinated
organic pesticides, brominated organic flame retardants and perfluorooctane
sulfonates (PFOS).

3.3 Eco-labels for Consumer Items

An eco-label is a logo that identifies a product that has met an environmentally
preferable standard. It is not always obvious what an eco-label means, and there are
Chemicals in Leather: International Trends on Risk-Based Control and Management 253

a high number of eco-labels available for leather. In many cases, the eco-labels have
been developed by a test institute or a group of test institutes who are responsible
for monitoring the compliance of these eco-labels. Typically, a company applies to
an eco-labelling organisation for the right to use its label on their products, and in
order to gain certification, the company and product must continually conform to
the required standards of the organisation. Some eco-labels consider only
the product (avoid toxic chemicals in the product), while others also take the
environmental impact during the production into consideration as well as the
quality and durability of the product.
It is sometimes difficult for a tannery to decide which eco-label is suitable due
to the high number of different schemes that exist on the market. In order for an
eco-label to be successful, it has to be recognised and used for consumer items. It
should also be noted that many of the eco-labels for leather are strongly textile
oriented and the criteria are sometimes more relevant for the textile sector.
The most relevant eco-labels for the leather industry are presented below.

3.3.1 Blue Angel (Der Blaue Angel)

The Blue Angel is a German eco-label for products and services [7]. The eco-label
was introduced in 1978 and was one of the first worldwide environmental labels.
The Blue Angel is an official label since it is owned by the Federal Ministry for the
Environment, Nature Conservation and Nuclear Safety in Germany. The award
criteria are established by the Federal Environmental Agency in Germany with the
support of scientific institutes and the industry.
Currently in 2012, the Blue Angel has around 80 product categories, and more
than 10,000 products have been awarded the Blue Angel. The Blue Angel has
developed two product categories that are relevant for the leather sector. These are
low-emission upholstery leather and footwear.
The Blue Angel eco-labels for leather may be awarded to the product “leather”
which has been manufactured in an environmentally friendly way, from the health
point of view does not have an adverse impact on the living environment and does
not contain any hazardous substances that would significantly impede recycling.
The criteria for the Blue Angel eco-labels go beyond legal provisions. The Blue
Angel eco-label includes a number of different criteria for leather which are related
to the following:
• Dangerous substances in the final product
• Water use during production
• Emissions from the production (COD, chromium, sulphide, AOX and toxicity)
• Durability of product
• Emissions of volatile organic compounds (VOCs)
• Consumer information
254 S. Rydin

3.3.2 EU Eco-label for Footwear (Previously Called the EU Flower)

The EU eco-label [8] was launched in 1992 when the European Community
decided to develop a Europe-wide voluntary environmental scheme that consumers
could trust. The EU eco-label covers a huge number of products and services. The
criteria are developed by key experts in consultation with main stakeholders in
order to decrease the environmental impacts over the entire life cycle of a product.
The criteria are revised every 4 years in order to take new developments and
knowledge into consideration.
The EU eco-label that is relevant for the leather industry is the eco-label for
footwear. The EU eco-label is given to consumer products. Leather is not in itself a
consumer product, but criteria for leather are included in the criteria for footwear.
The criteria can be found in Commission Decision of 9 July 2009 establishing
the ecological criteria for the award of the Community eco-label for footwear
(2009/563/EC).
The European eco-label for footwear includes a number of different criteria for
leather which are related to the following:
• Dangerous substances in the final product (chromium VI, arsenic, cadmium and
lead and free formaldehyde)
• Reduction of water consumption during production
• Emissions from the production (COD and chromium)
• Use of hazardous substances (PCP, TCP, forbidden azo dyes, SCCP and APE)
• Energy consumption (to be declared)
• Durability of product

3.3.3 The Nordic Eco-label Svanen

The Nordic eco-label is the official eco-label for the Nordic countries [9]. It
was founded in 1989 and the aim is to provide customers with a tool (the Nordic
eco-label logo) to help them choose among the best, environmental performing
products on the market. The criteria are developed by using a life-cycle perspective.
The Nordic eco-label has in total 63 product groups.
The Nordic eco-label has developed criteria for leather based on environmental,
health and quality requirements. The requirements are imposed on the production
process, from the production of skins to the final leather products. The Nordic
eco-label is to some extent coordinated with the European eco-label. The criteria for
the Nordic eco-label for leather are currently in 2012 being revised. At the moment
the Nordic eco-label for leather includes the following criteria regarding:
• Dangerous substances in final product (e.g. chromium VI, lead, cadmium,
formaldehyde and many other chemicals)
• Discharge to wastewater (COD and chromium)
• Use of hazardous chemicals (nonylphenol ethoxylates (NPE), PCP and many
other chemicals)
Chemicals in Leather: International Trends on Risk-Based Control and Management 255

3.3.4 Oeko-Tex 100

The Oeko-Tex Standard 100 [10] was introduced in the beginning of the 1990s. It
was developed by the Austrian Textile Research Institute (ÖTI) and the German
Research Institute Hohenstein and is a product label based on test for harmful
substances in leather (or textiles), and the primary target group is the textile and
clothing industry.
A tested product is allocated into one of four product classes based on its
intended use. The more intensively a product comes into contact with the skin,
the stricter the human toxicity requirement must be fulfilled by the product.
A certificate is issued and will be valid for 1 year and can be renewed.
The Oeko-Tex label tests for and restricts a high number of chemicals in the
product. It should be noted that chrome-tanned leather cannot receive the Oeko-Tex
Standard 100 certificate due to stringent demands on chromium. Since around
85–90% of all leather in the world is tanned with chromium, the certificate is
only valid for a minor part of the leather production.

3.3.5 SG Label

TÜV Rheinland in Germany was founded in 1872 and developed from a regional
testing agency to an international provider of services. TÜV Rheinland has developed
the SG Mark [11] which is a certification related to harmful substances developed
by TÜV Rheinland. This certificate only relates to chemicals in the product.
The objective with the certification is to ensure that the certified products present
no danger to human health to the best current knowledge. Furthermore, the product
undergoes testing and will continue to undergo random tests after the mark is
issued.
The testing includes test for prohibited azo dyes, pentachlorophenol (PCP),
formaldehyde and heavy metals.

3.4 Manufacturers and Brands

There are several international brands that publish their own lists of restricted
substances. Examples of brands are Adidas, H&M, IKEA, GANT and many
more. In many cases the lists from the brands are quite identical since they very
often are based on legislative demands from for instance the REACH legislation.
Also very often chemicals on the SVHC list will be included in the list of restricted
substances from the brands.
One sector which traditionally has been a driver regarding restriction lists for a
long time is the automotive industry. In particular, the automotive industry present
detailed specifications on many different chemicals and substrates. In the past, most
256 S. Rydin

of the different automotive industries had their own specifications and different
demands from different customers. However recently, the automotive industry has
started to cooperate regarding which chemicals that should be restricted and
declared. The European automotive industry has to comply with the End of Life
Vehicle Directive requirements and has set up a database to record each component
used in cars. To ensure that information on restricted substances is collected
worldwide, the global automotive declarable substance list (GADSL) has been
established and requires those in the supply chain to provide information for the
listed substance. The list contains 2,732 substances in 2011 and the GADSL list is
normally updated each year [1].
Also the automotive industry in other countries has started to produce restriction
lists. The Japanese automotive industry (JAMA) introduced in 2005 voluntary air
quality standards which limits the emissions inside cars.
Another initiative is the Leather Working Group (LWG) which is an initiative
with stakeholders in the leather industry including brands, manufacturers, suppliers,
NGOs and other end users. The LWG was formed in 2005. The group has
developed an environmental protocol for the leather manufacturing industry. The
group endeavours to promote improvement in the tanning industry by bringing
visibility to best practices and providing guidelines for continual improvement. The
LWG has developed an environmental assessment tool. The protocol provides a
framework of scoring structures that reward good environmental practice. The
scoring system enables those that perform better to achieve higher awards, and
tanneries can achieve gold, silver or bronze ratings. Some brands and end users use
this list as a sourcing tool to select preferred suppliers from the rated tanneries.
Furthermore, some recent initiatives from groups of companies in the Nordic
countries should be mentioned. Sweden Textile Water Initiative (STWI) started in
2010 as a joint project between textile and leather retail companies in Sweden. As
of November 2011, 32 companies have joined STWI. The aim of the STWI is to
produce guidelines for sustainable water management both for the textile sector and
the leather sector.
The STWI has produced guidelines for leather and textile production, and these
guidelines cover three areas which are water efficiency, water pollution prevention
and wastewater. The purpose of the water efficiency part is to ensure that only the
necessary amount of water is used in the factory reducing the size of wastewater
treatment plants as well as reducing energy and water costs. The areas of
water pollution prevention and wastewater aim to reduce negative health and
environmental impacts from chemicals used in the production processes. The
guidelines have divided companies into three categories which are level 1
(minimum level), level 2 (improver) and level 3 (achiever). The purpose of the
three-level structures is to facilitate continuous improvements and to enable
factories at all levels of performance to use the guidelines. The first version of the
guidelines was finalised and released in May 2012.
Another recent initiative in Sweden is the formation of Swedish Shoe
Environmental Initiative (SSEI) which is an initiative from the Swedish shoe
industry. The objective is to develop a sustainability index to be used primarily
Chemicals in Leather: International Trends on Risk-Based Control and Management 257

for development and purchase. The initiative started in 2012 and has so far gathered
more than 20 Swedish companies in the shoe sector. The development of a
sustainability index is expected to take around 3 years.

4 Restricted Chemicals with Relevance for the Leather Sector

There are, as mentioned in the previous section, a number of eco-labels and product
labels available on the market. Many of the requirements from different eco-labels
and RSL are similar, and some of the restricted chemicals are the same in the
different initiatives. A number of chemicals that very often are included in product
labels and list of harmful substances are presented below. This section only
describes some examples of chemicals that frequently are included in RSL, but
other chemicals will also be briefly included.

4.1 Aromatic Amines from Azo Dyes

Around 90% of all leather and textile dyes used are azo dyes. The azo dyes break
down during reductive conditions to form aromatic amines. Twenty two (22)
aromatic amines are forbidden in the EU Regulation 1907/2006 [5] since these 22
amines are known to be carcinogens or potential carcinogens. The focus on these
aromatic amines started in Germany, and in 1994 it became forbidden according to
the German Consumer Goods Ordinance to produce, import and sell garments and
fabric dyes with certain azo colourants (those azo dyes which can break down under
reductive conditions to release any of the 22 aromatic amines). Since the German
leather market is the most important market in Europe, all major chemical suppliers
of dyes very quickly substituted dyes containing prohibited azo colourants.
In 2002, the European Commission also prohibited the use of azo dyes which by
reductive cleavage of one or more azo groups may release one or more of the 22
amines. The dyes were prohibited according to the EU Directive 2002/61/EC from
July 2002 amending for the 19th time the Council Directive 76/769/EEC. This
directive was later replaced by Regulation EC 1907/2006 (REACH) according to an
EU Regulation from 2009.
Most of the commercially available azo dyes do not break down to produce these
forbidden amines. The European legislation which states that leather articles that
come into contact with human skin should not contain any of the 22 aromatic
amines in concentrations above 30 ppm can be found in Annex XVII [12] of
REACH. Furthermore, most eco-labels and RSL have the same criteria.
258 S. Rydin

4.2 Pentachlorophenol

PCP was widely applied by the leather industry before the 1990s for improving the
biocidal activity of raw hides and skins. Due to the risk of transformation into
dioxin during burning, the use of PCP and its salts and esters in leather
manufacturing is not allowed in the EU according to EU Regulation 1997/2006
(Annex XVII) [12].
Some member states in the EU like Germany, Austria and Denmark have in
addition implemented stricter legislation than EU and restrict the marketing of
leather products containing PCP and its salt and esters.
Furthermore, most eco-labels and restriction lists include PCP. PCP is also
discussed in connection with the Stockholm Convention on POPs and may be
restricted or forbidden worldwide through the Stockholm Convention in the future.

4.3 Chlorinated Paraffins (SCCP, Short Chain)

Chlorinated paraffins are very complex mixtures and are often divided into several
groups depending on the chain, length of the starting material and the amount
of chlorine in the final product. Three major groups are short-, medium- and
long-chained chlorinated paraffins (SCCPs, MCCPs and LCCPs).
Short-chained chlorinated paraffins (SCCP) are those with a chain length of
C10–C13. EU Regulation 1907/2006 [12] restricts the marketing and sale of SCCP
in preparations to a maximum of 1%. SCCP were mainly in the past used as
fatliquors, but other alternatives are available in the market. The use of SCCP is
also restricted by many eco-labels and RSL.
SCCP are just like PCP currently discussed in connection with the Stockholm
Convention on POPs and may be restricted or forbidden worldwide through the
Stockholm Convention in the future.

4.4 Chromium (VI)

Hexavalent chromium in leather products has become in focus during the last
10 years although the chemical is not used by the leather industry. Chromium
(VI) is known to cause severe allergic contact dermatitis in humans, is able to elicit
dermatitis at very low concentrations and is strongly suspected to be carcinogenic,
mutagenic and reprotoxic. Chromium (VI) is not used intentionally in the produc-
tion of leather but may be formed within the leather by oxidation of chromium (III)
used for the tanning of the leather. The mechanisms of the formation of chromium
(VI) in the leather are today well known, and measures for prevention of the
formation of chromium (VI) in measurable concentrations have been developed
Chemicals in Leather: International Trends on Risk-Based Control and Management 259

and implemented in most tanneries in the EU. The first survey of leather products
was made in Denmark in 2002 and revealed that around 30% of the tested leather
articles contained hexavalent chromium [13]. Recent surveys of chromium (VI)
in articles of leather in Germany and Denmark in 2007–2008 have demonstrated
that still more than 30% of the tested articles contained chromium (VI) in
concentrations above 3 mg/kg.
Denmark has in 2012 proposed that articles of leather, coming into direct and
prolonged contact with the skin, shall not be allowed to be placed on the European
market if leather contains chromium (VI) in detectable concentrations as measured
by ISO EN 17075:2007, with a detection limit of 3 ppm.
The Danish proposal for a European legislation is currently in 2012 on a public
consultation which ended on 16 September 2012. Two committees will present
opinions on the proposal which will be available by 16 March 2013. The
committees are for risk assessment (RAC) and socio-economic analyses (SEAC).
After this, the Commission will make a final decision regarding the proposal from
Denmark [14].

4.5 Dimethyl Fumarate

Dimethyl fumarate (DMF) is used by producers as a biocide to kill moulds that may
cause furniture or shoe leather to deteriorate during storage and transportation in a
humid climate. Placed in sachets, which are fixed inside the furniture or added to
the footwear boxes, DMF evaporates and impregnates the leather, protecting it from
moulds. However, it has been found to seriously affect consumers who were in
contact with the products. DMF penetrated through the clothes onto the skin of
many consumers. Cases of severe health problems have been reported in UK,
Finland, France and Poland. Although it is normally not used by tanneries, there
are examples where tanneries have used DMF.
The use of DMF in biocidal products was prohibited in the EU according to EU
Directive 98/8/EC [15]. However, the directive did not restrict the import of articles
treated with DMF into the EU. As a consequence, the European Union made a
temporary restriction to place products containing DMF on the market in 2009
(Decision 2009/251/EC). The restriction was on 15 May 2012 made permanent by
the EC Regulation 412/2012 amending Annex XVII to EC Regulation 1907/2006
(REACH) [12]. The text in REACH states that articles or any parts thereof in
concentrations greater than 0.1 mg/kg shall not be placed on the market.

4.6 Nonylphenol Ethoxylate/Nonylphenol

Nonylphenol (NP) has high aquatic toxicity and low biodegradability. Furthermore,
an extensive risk assessment showed that nonylphenol displays endocrine-
disrupting properties, i.e. hormone disrupting showing oestrogenicity. The use of
260 S. Rydin

products and product formulations that contain more than 0.1% of NP or NPE was
forbidden from January 2005 in the EU, and the ban is now incorporated in the
REACH legislation [12]. The only exception is in case of closed applications
systems where no release to wastewaters occurs.
NPE was previously used extensively as nonionic surfactants and emulsifiers in
both the textile and the leather industry but has now been replaced by alternative
surfactants in Europe. The main alternatives in the leather industry are linear
alcohol ethoxylates with different chain lengths and ethoxylation degrees. These
compounds are much easier than NPE degraded to non-toxic compounds. The
efficiency of linear alcohol ethoxylates as degreasing agents is comparable to that
of NPE.
The use of NPE is highly restricted in the EU but can still be found in leather
products imported from outside the EU. However, most eco-labels and restricted
substance lists restrict the use of NPE in the leather production.

4.7 Other Chemicals

Several other chemicals are often included in different RSL or eco-labels.
Examples of metals often included are lead, cadmium and arsenic. Lead and
cadmium may still be used as metal complex dyes but have in most cases been
substituted. Metal complex dyes are often used to increase the fastness properties of
leather, but metal complex dyes with lead and cadmium should be avoided.
Other chemicals that are common in different RSL are phthalates. Phthalates
are usually used as softening agents in plastics to obtain the required flexibility.
The most common phthalates included on restriction lists for the leather industry
are bis(2-ethylhexyl)phthalate (DEHP), benzyl butyl phthalate (BBP), dibutyl
phthalate (DBP), di-“isononyl” phthalate (DINP), D-“isodecyl” phthalate (DIDP)
and di-n-octyl phthalate (DNOP). All these chemicals are included on the SVHC
list (Candidate List), and currently (2012) there is a proposal to restrict the placing
of products containing DEHP, BBP and DBP on the market in the EU.
The use of biocides is in Europe controlled and regulated by the EU Biocidal
Products Directive [15]. Registration of a biocide is expensive and only a few active
biocide substances will in the future be available for the leather industry in the EU.
The directive will include a list of active substances that are permitted to use by the
leather industry (a so-called positive list). Many eco-labels and RSL does already
today include restrictions of the use of some biocides.
Perfluorinated chemicals such as PFOS and perfluorooctanoic acid (PFOA) are
usually restricted by brands and eco-labels. Furthermore, the EU regulates the
content of PFOS in consumer products on the market. The use of PFOS and
PFOA is also restricted by the Stockholm Convention on POPs although some
exemptions exist. PFOS are still produced and used in several countries and can be
used in the coating of leather.
Chemicals in Leather: International Trends on Risk-Based Control and Management 261

Finally, it should be mentioned that the automotive and upholstery industries
often introduce restrictions on the VOC emissions from leather. The VOC is
measured by heating the leather in a closed chamber, and the emitted VOCs are
determined by a mass spectrometer.

5 Conclusions

The leather industry is a traditional industrial sector using a high number of
chemicals as it is not uncommon that tanneries use 300–400 different chemicals
in their production.
Globally, it can be estimated that the tanning industry use around 3 million tons
of chemicals for the production of leather. The chemicals will end up in the product
or waste or will be directly discharged to the water, air or soil. Although a major
part of the chemicals are standard organic chemicals and standard inorganic
chemicals, it is important for tanneries to have a careful control of the chemicals
both for environmental and health reasons.
The main incentives for tanneries to implement a careful management of
chemicals are environmental legislation and production specification lists developed
by different customers. In addition, there are several voluntary eco-labels and product
labels on the market.
It is expected that due to legislation and increased customer awareness of the
content of chemicals in leather, an increased focus will develop on the use of
chemicals in the leather industry, especially regarding to the content of eventually
hazardous chemicals in the leather product.

References

1. Rydin S (2012) Risk management of chemicals in the leather sector: a case study from Sweden.
In: Bilitewski B et al (eds) Global risk-based management of chemical additives I: Production,
usage and environmental occurrence. The handbook of environmental chemistry, vol 18.
pp 207–224
2. Rydin S (2012) Chemicals in leather. Presentation at risk-based management of chemicals and
products in a circular economy at a global scale, Dresden, May 2012
3. European Commission (2012) Best available techniques (BAT) reference document for the
tanning of hides and skins – final draft June 2012. See http://eippcb.jrc.es/reference/BREF/
TAN_FD_06_2012.pdf. Accessed 15 July 2012
4. European Commission (2010) Directive 2010/75/EU of the European Parliament and of the
Council of 24 November 2010 on industrial emissions (integrated pollution prevention and
control)
5. European Commission (2006) Regulation No 1907/2006 of the European Parliament and of
the Council of 18 December 2006 concerning the registration, evaluation, authorisation and
restriction of chemicals (REACH)
262 S. Rydin

6. United Nations Environmental Programme (2009) Stockholm convention on persistent organic
pollutants (POPs) as amended in 2009
7. The Blaue Angel Eco-label. http://www.blauer-engel.de/en/index.php. Accessed 15 July 2012
8. European Commission, DG Environment Eco-label, see http://ec.europa.eu/environment/
ecolabel/. Accessed 15 July 2012
9. Nordic eco-label website, see http://www.nordic-ecolabel.org/. Accessed 15 July 2012
10. Oeko-Tex 100 Eco-label website, see http://www.oeko-tex.com/oekotex100_PUBLIC/index.
asp?cls¼21. Accessed 15 July 2012
11. TÜV harmful Testing website, see http://www.tuv.com/en/usa/services_usa/product_testing/
our_services/toxproof_1/toxproof.jsp. Accessed 15 July 2012
12. European Commission (2009) Regulation No 552/2009 of 22 June 2009 amending Regulation
(EC) No 1907/2006 of the European Parliament and of the Council on the Registration,
Evaluation, Authorisation and Restriction (REACH) as regards Annex XVII
13. Rydin S (2002) Investigation of the content of Cr(VI) and Cr(III) in Leather Products on the
Danish Market. Survey of Chemical Substances in Consumer Products, Danish EPA
14. European Chemical Agency, see http://echa.europa.eu/en/web/guest/view-article/-/
journal_content/a19f3846-4158-4351-8304-39de35c35f1b. Accessed 15 July 2012
15. European Commission (1998) Directive 98/8/EC of the European Parliament and of the
Council of February 1998 concerning the placing of biocidal products on the market (Biocidal
Products Directive)
Managing E-Waste in Developed and Developing
Countries

Suthipong Sthiannopkao

Abstract Electronic goods contain a range of toxic materials requiring special
end-of-life handling. This chapter surveys policies adopted by countries across the
spectrum of development to deal with waste from electronics and also practices that
now in fact exist for handling this hazardous waste. Developed countries have
conventions, directives, and laws to regulate the disposal of such e-waste, most
based on the extended producer responsibility concept. Manufacturers take back
items collected by retailers and local governments for safe destruction or recovery
of materials. Compliance, however, is difficult to assure, and frequently runs
against economic incentives.
The expense of proper disposal leads to the shipment of large amounts of e-waste
to China, India, Pakistan, Nigeria, and other developing countries. Shipment is
often through middlemen, and under tariff classifications that make quantities
difficult to assess. There, despite the intents of national regulations and hazardous
waste laws, most e-waste is treated as general refuse, or crudely processed, perhaps
by burning or acid baths, to recover only a few materials of value. Harm to the
environment, workers, and area residents is inevitable, often from release of
dioxins, furans, and heavy metals.
The faster growth of e-waste in the developing than in the developed world
presages continued expansion of an informal processing sector that, while on its
own terms is inexpensive and efficient, remains hazard-ridden.

Keywords E-waste, Extended producer responsibility, Informal waste processing,
Recycling, Take-back

S. Sthiannopkao (*)
Department of Environmental Engineering, College of Engineering, Dong-A University,
37 Nakdong-Daero 550 beon-gil Saha-gu, Busan, Republic of Korea
e-mail: suthisuthi@gmail.com

B. Bilitewski et al. (eds.), Global Risk-Based Management of Chemical Additives II: 263
Risk-Based Assessment and Management Strategies, Hdb Env Chem (2013) 23: 263–278,
DOI 10.1007/698_2012_195, # Springer-Verlag Berlin Heidelberg 2012,
Published online: 31 August 2012
264 S. Sthiannopkao

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
1.1 A Current Sense of Crisis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
1.2 Behind the Switch to Transboundary Shipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
2 Initiatives in Developed Countries Affecting E-Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
2.1 The Basel Convention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
2.2 EU’s Waste Electrical and Electronic Equipment Directive and RoHS . . . . . . . . . . . . 267
2.3 The 3Rs and StEP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
2.4 In the USA: Legislation and NGOs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
3 Policies and Systems in Developed Countries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
3.1 Registry, Collection, Logistics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
3.2 Take-Back in Japan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
4 E-Waste Policies and Handling in Developing Countries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
4.1 China . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
4.2 India and Pakistan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
4.3 Nigeria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
4.4 Other Developing Countries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
4.5 Nonrecovery of Valuable Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
5 Comparing E-Waste Management in Developed and Developing Countries . . . . . . . . . . . . . 274
6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276

1 Introduction

Electronic products become e-waste when they are deemed at the end of their useful
life. Nonfunctioning or obsolescent TVs, computers, printers, photocopiers, cell
phones, fax machines, home appliances, lighting equipment, games and such, when
no longer wanted, come to constitute e-waste. These electronic products contain
many materials requiring special end-of-life handling, most prominently lead,
mercury, arsenic, chromium, cadmium, and plastics capable of releasing dioxins
and furans.
The fate of e-waste is guided in vastly different ways, both physically and in
policy, in different parts of the world. Developed countries have gone to great
lengths to devise fairly complex, high-cost systems to handle e-waste, following
directives written to spare the environment – although the majority of e-waste
across Europe and North America still goes unrecycled [1]. Elaborate collection
systems are deployed, backed by information campaigns. Especially developed
clean recovery technologies are used, from disassembly stations to plasma furnaces
carefully engineered to prevent release of dioxins. In systems at the other end of the
scale, in developing and transition countries for which China, India, Pakistan, and
Nigeria may be taken as the archetypes, common practice is to smolder plastic off
cables, as the cheapest means known of recovering the copper. Precious metals may
be leached by acid baths from circuit boards and the used acid, laden with toxic
metals, dumped into the ground or nearby stream [2]. The surrounding population
may be largely unaware of any danger from toxicity.
Managing E-Waste in Developed and Developing Countries 265

Worlds apart are the practices, yet the official policies and regulatory guidelines
in developing countries show much influence from those of the developed world.
While waste import bans are common in the developing world, the topography of
recycling and disposal costs seems to assure a flow of e-waste out of the developed
world down to the points of lowest-cost disposal.
This chapter presents a characterization of the e-waste situation, particularly in
terms of intervention attempts made in order to manage it safely. The more
prominent agreements, policies, systems, and laws at the national and international
level are surveyed. Samples are provided of the environmental and human
consequences of large-scale movements of toxic e-waste to the developing world.
Trends for the next several years are noted, too.

1.1 A Current Sense of Crisis

The sense of crisis around e-waste arises from three considerations. The first is the
sheer volume of units of obsolescent electronics – recently 400 million items per
year in the USA alone, for example. Next is the fact of e-waste as a global
phenomenon, present nearly everywhere there are people. Finally, there is the
rate at which the e-waste volume is increasing, 5–10% yearly. China’s e-waste
will likely overtake the USA’s by the year 2020 [3]. India anticipates a growth from
about 400,000 tons in 2011 to 500,000 in 2012 [4]. Indeed, by the year 2030, the
developing world is forecast to discard twice the number of personal computers
annually as the developed world, some 600 million versus 300 million [5].
To insert a timely caveat, data for quantities of e-waste, particularly when
crossing borders, tend to exist in the form of estimates and be given as general
ranges; among the reasons is that most used electronics need not be specified as
such on tariff forms. E-waste, including functioning units, is typically shipped as
scrap plastic or metal and may also be mixed in a container with other types of used
goods, such as automobile parts [6].

1.2 Behind the Switch to Transboundary Shipment

The 1970s and 1980s saw the enactment in developed countries of wide-ranging
laws to manage the treatment of hazardous waste, along with other long-overdue
regulations of chemical use in the environment. When waste with hazardous
contents required special treatment and could no longer be simply dumped in
landfills, within a short time it became more economical to load materials
containing hazardous waste onto ships and trains for transport beyond the
boundaries and jurisdiction of those places in which they were produced or col-
lected. The containerization of shipping helped speed this change. Before the mid-
1980s, nearly all the hazardous waste produced in the USA stayed there, nor did that
266 S. Sthiannopkao

produced in industrialized continental Europe go far. Most was shipped either to
eastern Europe or the UK for processing [7]. However, the trend changed rapidly.
Between 1980 and 1988, for example, the number of companies seeking USEPA
approval to ship hazardous waste abroad rose from 12 to 522 [8].
Destination countries for this waste often welcomed the hard currency paid by its
senders. China, in the early 1990s, invited the arrival of containers of waste, the
government collecting a fee of US$50 per ton. A number of operators small and
large became established in the business of disposing of waste without possessing
the equipment or technology for safely processing it, and without regulatory
oversight. In the cheapest way possible, component materials of value were
removed, and the remaining matter disposed of by the most expedient means
available, generally by burying, burning, or discharging into waterways. By no
means was this an altogether new economic sector; an estimated 1% of the urban
population in developing countries engages in scavenging waste as a livelihood [9].
The crude processing of hazardous waste represents an extension of an existing
form of employment.
Egregious examples also occurred of hazardous materials disposed of abroad
with wanton disregard for safety, as, for example, when a landowner near the town
of Koko in Nigeria was induced by a shipper from Italy to allow the stacking of
barrels of highly toxic waste, some radioactive, on his property, in return for a small
monthly rent [10].
It was against the background of this trend to ship waste abroad that the impetus
for control of the transboundary movement of hazardous waste materials began in
the late 1980s and early 1990s. This need to address the large gap between
developed and developing countries in handing e-waste, both physically and in
the realm of policy, culminated in a variety of agencies putting forth initiatives.

2 Initiatives in Developed Countries Affecting E-Waste

2.1 The Basel Convention

The most important of these initiatives that would bear on e-waste was the Basel
Convention on the Control of Transboundary Movements of Hazardous Wastes and
their Disposal. The Basel Convention was intended to keep hazardous waste within
countries capable of safely handling it. For some time before it came into force in
1992, the OECD had seen the need for such an agreement. Environmental and
industry NGOs both contended at the time of the Convention’s negotiations to
influence its contents. The latter inveighed against further waste export restrictions
as stifling world economic growth. The political mood, however, and ultimate terms
of the agreement ran contrary to this position, according to Kempel [7], a delegate.
This most comprehensive agreement, with 178 nations party to it (signed, though
not yet ratified, by the USA), charges countries wherein hazardous waste is pro-
duced with responsibility for the safe disposal of such products, while banning
Managing E-Waste in Developed and Developing Countries 267

hazardous material exports to developing countries – except when written “prior
informed consent” from the accepting nation had been obtained. Extended producer
responsibility (EPR) is thus a core concept of the Basel Convention [11]. The
materials and their concentrations coming under regulation are defined in the
Convention’s Annex 1; these do not extend to functioning second-hand goods.
While it does provide rules for determining liable parties in cases of infringement,
penalties are not given, being left to individual states to enact.

2.2 EU’s Waste Electrical and Electronic Equipment Directive
and RoHS

The European Union WEEE (Waste Electrical and Electronic Equipment) Direc-
tive was written into law in 2003, and adapted by all member states by 2007. The
directive covers all types of electrical goods, for which it establishes ten categories,
and sets targets for their collection, recovery, and recycling. It notably calls for free
take-back of used products, as well as the establishment of collection points [12]. Its
sister directive is RoHS, “Restriction of Hazardous Substances.” This directive is
aimed at the design phase of products, and limits, by percent weight of homogenous
components, six specific materials: lead, mercury, cadmium, hexavalent chromium,
and two flame retardants added to plastics, polybrominated biphenyls (PBB) and
polybrominated diphenyl ethers (PBDE). The EU WEEE Directive and RoHS have
been influential in shaping legislation in other developed regions, such as Korea,
Japan, Australia, the USA, and Canada.

2.3 The 3Rs and StEP

The 3Rs “Reduce, Reuse, Recycle” Initiative was introduced by Japan at a 2004 G8
Summit. Japan has promoted use of the 3Rs domestically and on the international
stage. “Reduce” – preventing the creation of waste – is presented as the first
priority. Among this initiative’s other goals are furthering the technologies of
reuse, the cooperation of developed with developing countries on recycling and
reuse programs, and removing barriers to the international movement of materials
for recycling and remanufacture [13]. This last objective is seen by some as
conflicting with tenets of the Basel Convention, which stress producer-nation
responsibility.
Solving the E-waste Problem (StEP) is a UN-led initiative, organized in 2004, to
enhance and coordinate various efforts around the world on the reverse supply
chain, the reuse of recycled materials. Its five categories of concentration are policy,
redesign, reuse, recycling, and capacity building. The idea of redesign with disposal
in mind has growing promise [3]. One aspect is designing for ease and safety of
268 S. Sthiannopkao

eventual disassembly and recycling; another is design with minimal use of toxic
materials. In workaday terms, StEP organizes meetings and produces and
disseminates reports, all on a fairly large scale.

2.4 In the USA: Legislation and NGOs

While the US Congress has not yet ratified the Basel Convention, 25 of the 50 states
within the USA have enacted laws dealing with e-waste [14]. These state laws,
however, do not limit the international movement of electronic waste. Once e-waste
has reached even a state-approved collection agency, its fate is not easily traced,
and 50–80% of American e-waste has been reckoned to arrive in China, India,
or Pakistan [15]. Finally, in September, 2010, a national law was proposed in
the American Congress, known as the Responsible Electronic Recycling Act
(HR2284), an act designed to substantially control the shipment to developing
countries of waste electronics containing hazardous materials. The legislation is
expected to be passed by the US Congress [16]. HR2284 has fairly broad backing,
having been introduced jointly by one member from each of the major political
parties, and enjoys the support of the Electronics TakeBack Coalition (ETBC), as
well as companies such as Apple, Hewlett-Packard, and Samsung. It specifies a
comprehensive list of toxic substances banned from export, including CRTs (unless
broken and “furnace ready” for an already-designated recycler). Under the bill,
used goods for export need to be fully functional and tested as such within the USA.
HR2284 also funds a research initiative into recovery of rare earth materials [17].
Three American-based nongovernmental organizations have been particularly
active in e-waste issues. The Basel Action Network (BAN), Silicon Valley Toxic
Coalition (SVTC), and ETBC constitute an associated network of environmental
advocacy NGOs in the USA. They partner on the issue of international support for the
more strict export-limiting amendment to the Basel Convention known as the Basel
Ban. Promoting domestic collection and recycling is another joint cause, as is
investigative research – the fruits of which have considerably raised the profile of
BAN. Though an advocacy group, BAN, in its investigative role, has frequently been
the source of data cited in research papers and other media about e-waste issues.
The organizations’ common objective, in short, is promoting national-level
solutions for hazardous waste management [18]. One recent initiative has been
e-Stewards, a system for auditing and certifying recyclers and take-back programs
so that conscientious consumers know which ones meet high standards [19].

3 Policies and Systems in Developed Countries

The European Union and Japan have been leaders in formulating and then
implementing e-waste regulations. The Swiss are credited with establishing the
first comprehensive e-waste management system, covering collection to disposal.
Managing E-Waste in Developed and Developing Countries 269

In EU countries, the principle behind directives for collection, recovery, and reuse
has been EPR, making producers responsible for the take-back of e-waste. Canada
and Australia are among other countries developing systems based on these
principles. Japan’s “Reuse, Recycling and Recovery” system differs in some
ways, while still promoting take-back by manufacturers. The most salient differ-
ence is the direct payment of recycling costs by Japanese consumers.

3.1 Registry, Collection, Logistics

E-waste management in all these countries can be seen as consisting of three
elements: the national registry, the collection system, and logistics [3]. The national
registry is primarily a list of producers and their collection obligations; the registry
may be kept by a variety of agencies, which may also check compliance.
Systems for e-waste collection are usefully grouped into two types. A collective
system is usually nonprofit and nongovernmental, and founded by trade asso-
ciations, which concentrate on certain product categories for efficiency in finding
markets for reuse. In the clearing house system, producers, recyclers, waste
businesses, and such compete to provide services. The government sets the ground
rules for allocation and monitoring, and provides the national registry to a
coordinating body, from which that body may assign producer obligations; it also
establishes waste collection points.
Logistics of e-waste collection commonly involve three channels. Municipal
collection sites usually accept any amount of waste from citizens, without cost.
In-store retailer take-back schemes may be free or depend on repeat purchases.
Direct producer take-back is generally for business customers and may require a
replacement purchase.
Once collected, dismantling, preprocessing, and end processing are the stages
leading to safe disposal or recycling of e-waste. Dismantling and preprocessing
may be largely mechanical and require pneumatic wrenches and drills or other only
moderately specialized equipment. Worker training need not be extensive. End
processing by best available technology for metal recovery, a prime goal of e-waste
processing, does require a heavy investment, up to US$100s of millions. Integrated
metal smelters using extractive metallurgy to separate constituents are used for
complex items such as circuit boards. Highly skilled workers are needed [20].
Analyses of developed countries’ e-waste management shows Japan to have
perhaps the best-functioning system, in terms of scope and compliance levels.
Korea, Canada, and Australia have well-advanced systems as well. Switzerland’s
system is seen as a model of comprehensive management, and the Swiss, Norway,
Belgium, Sweden, and the Netherlands have all exceeded minimum EU e-waste
directives’ collection and recycling targets.
270 S. Sthiannopkao

3.2 Take-Back in Japan

Japan has had home appliance recycling laws since 2001, including for CRTs. The
end user has to pay a recycling fee, retail outlets provide collection points, and
recycling is by the producing company. For a fee, local governments will also
collect the goods to be disposed of. Recycling fees paid by consumers range from
about 1,800 to 5,000 yen (about US$20–55), depending on the type of item. In the
absence of a producer company to take back goods, another company is designated
for that role. In this way about 74% of e-waste reaches a recycler [21], compared to
a US average of about 12.5% [22]. Domestic recycling follows best practices, such
as the careful separation of materials, decontamination, step-by-step disassembly,
and destruction of some components by plasma arc furnaces, to not release toxic
compounds.
Many computer and other IT device makers offer take-back programs even
where not mandated by law. In the USA, Apple, Sony, Sharp, Mitsubishi, Samsung,
Hewlett-Packard, Dell, LG, Lenovo, Panasonic, and Toshiba have free collection
point or mail-in take-back programs of their products. Apple and Hewlett-Packard
provide some form of payment for the value of the taken-back item. Other
companies, Hitachi, Phillips, and Funai, do not now have take-backs [23].

4 E-Waste Policies and Handling in Developing Countries

The policies and systems just outlined notwithstanding, a great portion of waste from
developed countries is sent for processing or disposal to the developing world. China,
India, Pakistan, and Nigeria have become the leading destinations. While all four are
parties to the Basel Convention and have other forms of regulations intended to
address the importation of hazardous waste, shippers and waste processors find it
possible to transport waste labeled, for example, as used goods, which the Basel
convention does not cover, in order to get it landed. The enforcement of rules bearing
on the import or handling of e-waste is generally not seen as a priority by the local
enforcers, who can often be induced to overlook transgressions [24].

4.1 China

China, in addition to ratifying the Basel Convention, has a 2002 law banning
hazardous waste imports. In 2005, the Management Measure for the Prevention
of Pollution from Electronic Products became effective. It has been referred to as
China’s RoHS, specifying limits on materials similar to the EU Restriction of
Hazardous Substances directive. A new waste disposal law enacted in 2009,
Regulations for the Administration of the Recovery and Disposal of Electric and
Managing E-Waste in Developed and Developing Countries 271

Electronic Products, targets e-waste more specifically, by funding safe electronic
recycling facilities. Manufacturers, retailers, and recycling companies are to be
responsible for collecting and safely handling e-waste, and recyclers are to be
licensed. Obligations and penalties, however, are loosely defined in the law’s
wording [25].
An archetype of “backyard” e-waste processing is Guiyu, a set of towns in
southeast China. Guiyu had become a major imported e-waste processing area by
1995, and has about 5,500 shops employing around 150,000 people [26]. The
majority of the workers come from elsewhere in China. They typically labor
without goggles, gloves or proper ventilation, indeed without basic personal
safeguards. Many are minors. Fengjiang, south of Shanghai, is another large
processing area, handling mainly domestically produced e-waste.
Consumers in Japan or other developed countries may pay to have e-waste
collected; in China a component of the informal processing system is circulating
peddlers who pay householders for unwanted electronics, after a bit of doorstep
haggling. Chi et al. [27] cite this as an example of the efficiency of the informal
system: the peddlers take care of collection and transportation as part of a self-
organizing, demand-driven system that continuously sets market values for e-waste.
They do not consider a prohibition of the informal sector as practical. Backers of
this pragmatic approach see that while government and private sector investment
for formal processing systems is growing, such systems will not match the reach,
efficiency, and volume of the pervasive and cheap informal sector. Investment
should therefore also be made in workable basic technical solutions to ameliorate
polluting aspects of informal e-waste processing.

4.1.1 Human Effects of E-Waste in Guiyu

The vast amount of waste electronics processed in Guiyu over a relatively long
period has made it a prime area for investigating the effects of crude e-waste
disposal methods on the air, water, soil, and people. Leung et al. [28] took soil
samples where it had long been common to burn such things as cable sheathing to
recover copper wire, and to use open-pit acid leaching for separating metals of
value. Their study focused on polybrominated diphenyl ethers and polychlorinated
di-benzo-p-dioxins along with dibenzofurans, that is, PBDEs and PCDD/Fs. In
duck ponds and rice paddies, these carcinogens were found in levels exceeding
international guidelines for agricultural areas. China itself has not yet set such
guidelines for these materials. Wong et al. [29], in their 2007 study of the Guiyu
area, looked at a wide variety of pollutants in the soil, air, and water, and measured
high levels of air-borne PBDE dioxins and polycyclic aromatic hydrocarbons. Their
presence is attributed to incomplete combustion of plastic chips, insulation, and
PVC materials. Elevated levels of heavy metals were found in sediments near
paddies – and commonly grown rice cultivars, it should be noted, have, among
all plants, an exceptionally high capability for taking up and concentrating cad-
mium [30]. Li et al. [31] have found umbilical cord blood cadmium levels above
WHO standards in over 25% of neonates in the Guiyu area.
272 S. Sthiannopkao

4.2 India and Pakistan

India is second to China in processing e-waste. Seventy percent of the e-waste
processed or disposed of in India is believed to originate abroad, with Delhi as its
primary destination. Bangalore handles more that is domestically produced; India
by itself produces 400,000 tons of e-waste annually. With only three facilities
currently existing in India to properly handle e-waste, the overwhelming majority
goes into the informal sector. As in China, unwanted electronic equipment is seen
as worth money, and sold by households or businesses to doorstep collectors.
Wath et al. [32] point out that India lacks actual legislation dealing with e-waste.
The Ministry of Environment and Forests (MoEF) issues rules and guidelines for
waste management; those bearing on e-waste are the 2004 “Municipal Solid Waste
Management Rules” and the 2008 “Hazardous and Waste Management Rules.”
More specific new regulations, codified as the “2010 E-waste Management and
Handling Rules,” become effective in 2012. These set hazardous substance limits
on lead, mercury, cadmium, hexavalent chromium, PBBs, and PBDEs, that is, the
six RoHS materials. Also called for are collection centers and EPR rules for
recycling [33]. By judicial ruling, the import of e-waste into India is considered
illegal. In practice, this ruling seems easily evaded through such dodges as labeling
e-waste as charitable donations, scrap metal, or reusable products [34]. The net
effects of the ministerial regulations and judicial rulings on the informal recycling
sector, or on the e-waste illegally imported each year, are likely to be modest.
Research near Bangalore [35] into the effects of crude disposal processes on the
environment and workers found elevated levels of trace elements Cu, Zn, In, Sn, Pb,
and Bi in soil near informal recycling shops. Among the workers, hair samples held
high levels of Cu, Sb, Bi, Cd, and Ag.
Pakistan has also emerged as a major destination for e-waste, receiving large
volumes from the EU, Australia, and the USA, with transshipment often through
Hong Kong or Singapore. Pakistan has ratified the Basel Convention, and has
produced its own waste legislation. Pakistan’s Environmental Protection Act of
1997 prohibits the import of hazardous waste. The National Environment Policy of
2005 and Import Policy Order of 2009 further define and restrict hazardous materials.
Despite this policy framework, a large recycling industry imports what is commonly
but inaccurately labeled as second-hand equipment. All but of a small percentage of
the imported used electronics are dismantled as electronic scrap – for example, only
2% of imported used computers are reused. Dismantling is by crude methods, by
hand rather than by machine, by workers with no protective gear. Lead, cadmium,
barium, mercury, chromium, and other toxic elements are released into the environ-
ment, as there is no formal system in place to handle the quantities produced [36].

4.3 Nigeria

Nigeria is a major destination for e-waste from Europe and Asia. Attention was
drawn to Nigeria and to Africa in general as a victim of e-waste in the 2005 BAN
Managing E-Waste in Developed and Developing Countries 273

documentary “The Digital Dump” [37]. An earlier attempt to bring attention to the
problem of Africa as a too-acquiescent waste destination was a convention held in
Bamako, Mali, in 1991. Representatives of 51 Organization of African Unity (now
African Union) countries, on the grounds that the work in Basel would still allow
too much waste past their borders, passed the Bamako Convention as a supplement
to the Basel Convention. It was markedly more restrictive, in casting a wider
definition of what was hazardous then nearly categorically banning the import of
such, with transgressions to be viewed as criminal acts. Although Bamako officially
came into came into force in 1998, calls to use it against e-waste have had not
produced results [38]. The value of Bamako may be said to be that it is an already
extant piece of regulation with at least the potential for use: the stimulus that
occurred to produce it may not come again.
Nigeria has as well its Harmful Wastes Act, which, rather than listing banned
substances, broadly bans materials by their effects, defining such materials as those
which “. . .subject a person to risk of death or. . .incurable impairment.” Trading in
such can be punished by life imprisonment [39]. Nigeria’s more recent National
Environmental Regulations (Electronics Sector) explicitly prohibits unusable elec-
tronic goods [40].
Poorer countries are the natural market for working used electronics, and it has
been estimated 500 shipping containers of used electronics enter Lagos, Nigeria
each month [37]. Each container can hold about 350 large televisions, or about 800
computer monitors or CPUs. In reality, most of this used equipment will not be
functionable. To characterize the situation, if a shipper wishes to remain on good
terms with the receiver, the container will include enough functioning items to
allow the receiver a decent profit after covering shipping costs [6]. A representative
of the Nigerian electronics trade group CAPDAN thought up to 75% of a container
might be junk electronics the recycler wanted to be rid of, perhaps to avoid high
home-country recycling costs. These were commonly dumped in swampland out-
side Lagos, there to be picked over by scavengers. Unlike in Guiyu, there seems
here to be little extraction of metals by acid leaching. Most pollution comes from
burning insulation from wires and cables, or igniting the vast piles of televisions
and computers, to reduce the piles’ size [6]. Even for the resold usable products,
their fate at the end of their second life is, very likely, to be added to the pile in the
swamp.

4.4 Other Developing Countries

The e-waste situation in China, India, Pakistan, and Nigeria can be found, on
smaller scales, in a surrounding swath of countries, including Bangladesh,
Cambodia, Ghana, Indonesia, Malaysia, Sri Lanka, Thailand, and the Philippines.
Among these there is currently a rather low level of imported e-waste: though to the
degree that China manages to restrict its intake of e-waste, the likely effect is a
corresponding deflection of waste to nearby developing countries, to undergo crude
processing.
274 S. Sthiannopkao

Most local e-waste in these countries is seen as having a positive money value, and
is thus pulled by the small profit to be turned at each step through an informal
recycling network that collects, trades, transports, and processes it. Collecting, a low
barriers-to-entry vocation, is quite thorough for e-waste of any value. Most all the
system operates outside the guidance of regulations [3]. The legal framework bearing
on e-waste in these states is nearly always in the form of department-issued regulatory
guidelines rather than statutes specifically for electronic waste (e.g., in Malaysia
[41]). Table 1 shows the dispositions of several developing Asian nations regarding
the regulations, inventories, collection, and processing of e-waste [3, 42, 43].

4.5 Nonrecovery of Valuable Metals

Electronic equipment today makes use of many precious and special metals; its
manufacture has therefore become an important contributor to world demand for
metals. Developed countries, particularly in the EU, have sought to establish through
legislation a circular flow economy to preserve such valuable resources. Neverthe-
less, most are lost, and the primary reason has been the vast, often illegal outflow of
e-waste to developing and transition countries lacking recycling infrastructure. The
crude recovery methods of the developing world get at the most easily recoverable
high-value metals, usually copper and very small amounts of gold, of which the
typical cell phone has 24 mg, and silver (250 mg). Other rare metals with a soaring
demand in electronics, such as indium, ruthenium, and palladium, are lost among the
tons of waste because low-tech methods cannot recover them [44].
In addition, these precious and special metals have very low concentrations in
ores; mining, smelting, and refining these metals therefore have a particularly large
environmental impact. Recovering these metals from defunct electronic equipment
would result in a fraction of the effect on the environment [20].

5 Comparing E-Waste Management in Developed
and Developing Countries

In terms of the three elements, a national registry, a collection system, and logistics
that constitute e-waste handling in developed countries, what do we find in devel-
oping countries? A national registry keeping track of produced electronics for the
purpose of eventual manufacturer take-back is in a nascent stage in China and India.
For developing countries, a first step is to make an inventory of e-waste. Abbas [36]
reports such inventorying is essentially not done in Pakistan. India has set and run
trials on an inventory system during the past decade [4], but it has not reached an
effective usage level [45]. China has committed to making an e-waste inventory. Its
new e-waste law, effective in 2011, does call for a government-maintained cata-
logue of electronic items domestically produced [46]. Collection of most e-waste
remains in the hands of the informal sector in the developing world. In China and
India, its separation from general refuse is in the hands of local recyclers.
Table 1 Regulations and management strategies for e-waste in some developing Asian countries
Levels 1 2 3 4
Practice Rudimentary Best
Legal Legal framework nonexistent or A legal framework to be issued/ Some enforcement, but the legal Full enforcement and model legal
framework only as plan enforced in the near future framework is not uniformly framework for other countries
conducted
Cambodia, Bangladesh, Sri Lanka, India China, Malaysia, Thailand –
Vietnam, Indonesia,
Philippines
Inventory There is an inventory for An e-waste inventory is under E-waste inventory is conducted, E-waste inventory is fully
municipal solid waste, but planning and preparation but has lack of information and conducted and publicly
no designated inventory for data. available
e-waste
Sri Lanka, Bangladesh, China, Thailand, Indonesia, Cambodia, India –
Vietnam Philippines, Malaysia
Separate Unregulated pick-up of e-waste E-waste is well collected by local A collection system for e-waste is Collection systems are fully
collection of value only, by local collection mechanisms. Pilot operational and leads to operational. Collection is
of e-waste collectors separation and collection environmentally sound recognized as a model system
Managing E-Waste in Developed and Developing Countries

systems have been set up disposal by other countries
Cambodia, Bangladesh, Sri Malaysia, China, Thailand, India – –
Lanka, Vietnam, Indonesia,
Philippines
Recycling Only recyclable and reusable There is a plan to set up e-waste There are e-waste recycling State-of-the- facilities can
technology e-waste is recycled and facilities facilities, which accommodate accommodate all e-waste in
reused, by local a minority of all e-waste in the the country
stakeholders country
Sri Lanka, Indonesia, – China, Thailand, India, Malaysia –
Philippines, Cambodia,
Vietnam, Bangladesh
Adapted from [3]
275
276 S. Sthiannopkao

In both China and India (and to a lesser extent in Pakistan) some facilities have
been built enabling the proper technology for e-waste disposal. Among these
countries, China at least possesses a large capacity in such things as the smelting
furnaces needed for recycling nonferrous metal. China is thus seen as the large-
scale handler of e-waste that, with the help of partnering and technology transfer,
has the potential for building facilities for handling a significant amount of it
properly [20]. The vast scale of e-waste both imported and domestically produced,
its rate of increase, cost of transport, and above all the high cost of facilities for its
benign disposal, indicate that, despite the adoption of tighter official regulations in
China, India, Pakistan, and Nigeria, their informal sectors will continue to handle
the great majority of e-waste.

6 Conclusions

In developed countries, e-waste is collected to recover some materials of value and
to be safely rid of the lead, cadmium, mercury, dioxins, furans, and such toxic
materials as they contain. In developing countries, e-waste is collected principally
to recover a few metals of value.
Major e-waste importing countries have laws restricting hazardous waste
imports. The policies of developed countries in this area have served as models
for official policies in the developing world. Developing countries, however, harbor
in their economies an entrenched sector, in several respects honed to a high degree
of efficiency, whose profitability depends on the retrieval of material from e-waste
using methods harmful to the environment.
The direct release of toxic materials into the environment by the burning,
burying, dumping, or discharge into waterways of the by-products of crude
recycling methods will likely make zones where this work is done unsafe for
habitation. Those living in such areas or working with the waste without protective
equipment will risk the effects of exposure.
The faster rate of growth of e-waste produced in the developing world than in the
developed world likely means that by the year 2018, more e-waste will be produced
in places unable to process it properly than in places that can [5]. Where it exists as
an efficient and pervasive bottom-up market-driven system, the informal sector
may best be reformed by specifically targeting its most dangerous practices.

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Mass Emissions of Pollutants from E-Waste
Processed in China and Human Exposure
Assessment

Hong-Gang Ni and Eddy Y. Zeng

Abstract Electronic waste (e-waste) has become a pressing global pollution issue.
The situation in China is more severe, due to largely primitive recycling of e-waste
generated domestically and imported from outside China. In China, the improper
e-waste recycling operations have resulted in severe contamination of the ambient
environments by toxic pollutants. All data suggest that the contaminant levels in
various environmental media near e-waste recycling sites are substantially higher
than those at reference sites. People living near e-waste recycling sites and adjacent
regions are subject to increased health hazard. Long-range transport of e-waste-
derived pollutants can also subject residents in adjacent regions to unintended
health risks. Given the special circumstances in China, implementation of improved
e-waste recycling technologies and rigorous law enforcement should be the ulti-
mate resolution for containing the spreading of e-waste-derived pollution.

Keywords China, Electronic waste (e-waste), Human exposure, Mass emission,
Pollutant

Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
1.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
1.2 Central Issue . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
1.3 Scope and Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282

H.-G. Ni
Shenzhen Key Laboratory of Circular Economy, Peking University Shenzhen Graduate School,
Shenzhen 518055, China
E.Y. Zeng (*)
State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry,
Chinese Academy of Sciences, Guangzhou 510640, China
e-mail: eddyzeng@gig.ac.cn

B. Bilitewski et al. (eds.), Global Risk-Based Management of Chemical Additives II: 279
Risk-Based Assessment and Management Strategies, Hdb Env Chem (2013) 23: 279–312,
DOI 10.1007/698_2012_189, # Springer-Verlag Berlin Heidelberg 2012,
Published online: 31 August 2012
280 H.-G. Ni and E.Y. Zeng

2 Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
3 Disposal of E-Waste in China . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
3.1 Importation and Domestic Generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
3.2 Procedures of Disposal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
4 Emissions of Pollutants from E-Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
4.1 Organic Pollutants from E-Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
4.2 Heavy Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
4.3 Mass Emissions of Organic Pollutants from E-Waste in China . . . . . . . . . . . . . . . . . . . . . 295
5 Human Exposure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
5.1 Exposure to Organic Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
5.2 Exposure to Heavy Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
6 Future Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
Lists of Organic Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 307

1 Introduction

1.1 Background

The main aims of this chapter are to provide estimates for the amounts of pollutants
emitted from processed electronic waste (e-waste) and assess the magnitudes of
human exposure to these pollutants. Specifically in this chapter, e-waste is defined
as the sum of discarded personal computers, electronic/electrical equipment, elec-
tronic entertainment devices, cell phones, television sets, and refrigerators. In
another word, e-waste explicitly refers to electronics at their end of life cycle and
disposed by end users rather than surplus electronics (brand new products). In
addition, e-waste also does not include reusable (e.g., repairable electronics or
second hand electronics) and secondary scraps (e.g., noble metals, plastics, and
rubbers).
The global demand for electronic equipment has continued to grow in recent
years. Various electronic products, such as household electronic appliances,
telecommunications equipment, and consumer electronic goods are in increasing
use. Again, fast growing amounts of surplus electronics around the globe continue
to be generated with rapid advances in technology, falling prices, and planned
obsolescence. For example, approximately 30 million computers are discarded in
the USA and 100 million phones are disposed of in Europe each year. The U.S.
Environmental Protection Agency (USEPA) estimated that only 15–20% of e-waste
is recycled, while the rest goes directly to landfills and incinerators [1]. Apparently,
disposal of e-waste is becoming an increasingly challenging task around the world
[2]. Technical solutions are available but in most cases a legal framework, a
collection and transport system, and other logistics need to be implemented before
a technical solution can be applied. Besides, to avoid costly treatment processes,
some exporters deliberately transport difficult-to-recycle e-waste to other regions
such as developing countries rather than recycling by themselves.
Mass Emissions of Pollutants from E-Waste Processed in China and Human. . . 281

In addition, the concern about e-waste not only focuses on its vast quantity
generated daily, but also more on the need to handle the toxic chemicals embedded
in it. It is well known that e-waste contains lead, beryllium, mercury, cadmium
(Cd), and brominated flame retardants (BFRs) among other chemical materials [3].
Furthermore, highly toxic chemicals such as polychlorinated dibenzo-p-dioxins
and dibenzofurans (PCDD/Fs) and polybrominated dibenzo-p-dioxins and dibenzo-
furans (PBDD/Fs) can be formed during the recycling process [4].
Although China has officially banned e-waste importation, such ban in some
cases has resulted in underground illegal e-waste trading activities. In fact, e-waste
problems are not limited to China alone; other developing countries such as India,
Cambodia, Indonesia, Pakistan, Thailand, and Nigeria also have to deal with similar
issues [2, 5].

1.2 Central Issue

China generates a large portion of the world’s e-waste and gradually pollutes its
environment in the process. The most urgent issue related to e-waste in China is the
widespread use of primitive recycling methods, which has resulted in intensive
environmental and human exposure to toxic chemicals released during the
recycling processes and caused possibly severe environmental and human health
hazards [6–9]. One example is the likelihood for e-waste processing workers to be
readily exposed to toxic chemicals derived from e-waste. Moreover, e-waste
processing workers may unintentionally carry hazardous materials home on their
skins and clothing, subjecting their families to unintended exposure [10].
Several groups of e-waste-derived toxic chemicals, which have gained world-
wide attention in recent years, include halogenated polycyclic aromatic
hydrocarbons (such as chlorinated polycyclic aromatic hydrocarbons; ClPAHs),
BFRs, dioxins and dioxin-like compounds, and heavy metals. Among them, BFRs
and metals are embedded materials, whereas halogenated and parent PAHs and
dioxins/dioxin-like compounds are produced during recycling processes. As the
main components of BFRs, polybrominated diphenyl ethers (PBDEs) can lead to
impaired learning and memory functions. Meanwhile, PBDEs can also interfere
with thyroid and estrogen hormone systems [7, 11]. Dioxins or dioxin-like
compounds are comprised of three structurally related families of chemicals:
PCDDs, PCDFs, and polychlorinated biphenyls (PCBs). These compounds have
caused considerable concerns because of their acute toxicity. Finally, some
halogenated PAHs have been shown to elicit dioxin-like toxicity and mutagenic
properties [12].
Manufacture of cell phones and personal computers consumes 3% of gold and
silver mined worldwide each year, and 13% of palladium and 15% of cobalt as well.
Electronics contain approximately 60 elements, some valuable and hazardous, or
both [13]. Recycling the valuable elements is the driving force behind the intensive
activities engaged in disposal of e-waste.
282 H.-G. Ni and E.Y. Zeng

Recycling of printer circuit boards is deemed as the most important source of
heavy metals to the ambient environment. These heavy metals may be entering into
human body from various exposure routes such as ingestion, inhalation, and dermal
absorption. Exposure to high levels of heavy metals can lead to acute and chronic
toxicity, such as damage to central and peripheral nervous systems, blood compo-
sition, lungs, kidneys, liver, and even death [14].

1.3 Scope and Objectives

The e-waste issue can be discussed from multiple angles, e.g., international trade,
management, and recycling techniques. This chapter is intended to address the
environmental consequences of e-waste disposal if not conducted properly.
Our recent review [15] has summarized data related to environmental and human
exposure to persistent halogenated compounds derived from e-waste in China.
However, no information on heavy metals derived from e-waste recycling
processes was given in that review. In addition, numerous studies carried out in
China in recent years have surveyed the environmental occurrence of organic
pollutants [16–21] and heavy metals [22–25] derived from e-waste recycling
activities, which provides sufficient data for another integrated assessment of the
e-waste issue in China. Therefore, this chapter will summarize the concentration
ranges of organic pollutants and heavy metals in various environmental media near
e-waste contaminated and reference sites in China. Based on this information, mass
emissions of organic pollutants from e-waste processed in China will be estimated,
and the magnitude of human exposure to e-waste-derived pollutants will be
assessed as well.

2 Approach

To obtain the mass emissions of pollutants from e-waste recycling processes, it is
essential that the inputs of pollutants are truly e-waste related. To fulfill this
requirement, a causal analysis is desirable. However, the concept of causation is
rather problematic because causal mechanisms are complex [26]. Nonetheless, we
are compelled to identify causes, in an attempt to minimize the uncertainties
associated with our estimates. In this chapter, the strict empiricist, David Hume’s
empirical criterion, was adopted. This approach requires only a combination of
(1) e-waste processing and environmental pollution are associated in space and time
(contiguity); (2) e-waste processing precede to environmental pollution (temporal
succession); and (3) e-waste processing is always conjoined with environmental
pollution (consistent conjunction). These are always the cases judged from a
number of previous studies [6, 27–35].
Mass Emissions of Pollutants from E-Waste Processed in China and Human. . . 283

Fig. 1 Map of the main sampling locations mentioned in this chapter

Many reports have demonstrated serious environmental impacts from e-waste
recycling activities in developing countries and regions [6, 27–35]. Previous studies
conducted in Taizhou of Zhejiang Province [33] and Guiyu of Guangdong Province
[36] have confirmed that improper e-waste recycling operations do lead to serious
environmental pollution in surrounding areas (Fig. 1). However, e-waste recycling
processes are not necessarily the only cause for the environmental occurrence of
some pollutants (e.g., BFRs and heavy metals) as other sources than e-waste
recycling may also be present. To our best knowledge, no definitive evidence is
available to implicate that e-waste recycling processes are the exclusive sources of
BFRs, dioxin-like chemicals, or heavy metals. It should be noted that although
numerous studies on the occurrence of PBDEs and PCDD/Fs in Chinese soil have
been published, only a few reports have focused on soil impacted by e-waste
recycling.
It is expected that soil PBDEs and PCDD/Fs may also have stemmed from other
sources than e-waste recycling processes, as only 3% of the global production of
flame retardants is used in electronic products [36]. Apparently, only a small
portion of BFRs occurring in the environments is derived from e-waste.
284 H.-G. Ni and E.Y. Zeng

Nevertheless, various toxic chemicals can be released into the ambient environ-
mental media during primitive e-waste recycling processes [2, 3, 37, 38]. Because
e-waste recycling is intended to recover noble metals such as copper (Cu) and gold
[39], e-waste-derived metal pollution is inevitable and should also be investigated.
In fact, several reports or reviews on metal pollution from e-waste in China have
been published [2, 14, 17, 24, 36, 40, 41]. However, these previous studies only
investigated metals in the environmental media around e-waste recycling sites, and
no control sites were involved. Consequently, it is difficult to assess the impacts of
e-waste recycling processes on the environment.
Because causation of e-waste and pollutants is very difficult to identify as
mentioned above, comparative analysis between e-waste and non-e-waste sites is
a suitable choice for identifying the environmental impacts from e-waste recycling
processes. To achieve this goal, we chose several typical e-waste recycling sites in
China as the target regions to conduct comparative analyses. Data acquired from
various environmental media near several major e-waste recycling sites and control
sites in China were subject to comparative analysis.

3 Disposal of E-Waste in China

3.1 Importation and Domestic Generation

Importation from developed countries and domestic generation are two main
sources of e-waste in China. According to a report by the United Nations Environ-
ment Programme (UNEP), “Recycling – from E-Waste to Resources” [13], the
amounts of e-waste generated from obsolete computers, cell phones, and televisions
by 2020 in China will be approximately 4, 7, and 1.5 times, respectively, higher
than the levels in 2007. If classified by device type, the estimated amounts of
e-waste currently generated in China are 0.3 million tons from personal computers,
0.5 million tons from refrigerators, and 1.3 million tons from television sets,
resulting in 2.1 million tons/year as the total amount of e-waste generated domesti-
cally. This figure is considerably similar to another estimate of 2.3 million tons,
which makes China as the world’s second largest producer of e-waste behind the
USA (approximately 3 million tons/year) [13].
Worse yet, China has been a major dumping ground of e-waste from developed
countries despite the fact that e-waste importation has been declared illegal [42].
In fact, importation of e-waste to China has been lasting for more than 10 years and
is still underway. Of the huge amount of e-wastes generated worldwide each year,
70% is being exported to China [43]. Notably, only public information, such as
data from official documents and reports or peer-reviewed publications, is used in
this chapter. As the main recipient of e-waste, Guangdong Province usually
receives the majority of imported e-waste, and then diverts some of it to other
provinces or municipalities such as Hunan, Zhejiang, Shanghai, Tianjin, Fujian, and
Shandong (Fig. 1).
Mass Emissions of Pollutants from E-Waste Processed in China and Human. . . 285

Fig. 2 Abridged general view of environmental and human exposure to e-waste-derived
pollutants in China

3.2 Procedures of Disposal

The biggest concern about e-waste is obviously the release of embedded toxic
chemicals to the environment, and a secondary concern is regarding the use of
unhealthy and environmentally damaging methods for dismantling electronics to
recover useful and valuable materials. As shown in Fig. 2, most methods for
recycling and disposal of e-waste in China are primitive. For example, dismantling
of e-waste often takes place with bare hands with no protection. Other unsafe
practices include cathode-ray tube cracking and dumping, circuit board recycling,
acid stripping of chips, plastic chipping and melting, and dumping of waste
residues [2, 5]. To recover copper from e-waste, for instance, wires are pulled
out, piled up, and burned. This emits dioxins and other pollutants [42]. Toxic
cyanide and acids used to remove gold from computer circuit boards are also
released into the environment [42]. These methods are able to not only recover
gold, platinum, and other valuable materials but also unleash toxins to the
surrounding environment.
There are many e-waste disposal sites in China, among which Guiyu of
Guangdong Province (Fig. 1) is a focal point of international attention as it is
286